PDF The Organotransition Metal Chemistry of Poly Pyrazolyl Borates Part 1 First Edition Fink Download

Full download ebook at ebookname.
com
The organotransition metal chemistry of poly

pyrazolyl borates Part 1 First Edition Fink
https://ebookname.com/product/the-organotransition-metal-
chemistry-of-poly-pyrazolyl-borates-part-1-first-edition-
fink/
OR CLICK BUTTON
DOWLOAD NOW
Download more ebook from https://ebookname.com

More products digital (pdf, epub, mobi) instant
download maybe you interests ...
The Survey Kit 2nd edition The Survey Handbook 1 Dr.

Arlene G. Fink
https://ebookname.com/product/the-survey-kit-2nd-edition-the-
survey-handbook-1-dr-arlene-g-fink/
The Greek State at War Part 1 The Greek State at War

Part I
https://ebookname.com/product/the-greek-state-at-war-part-1-the-
greek-state-at-war-part-i/
Role of Poly Vinyl Chloride in Healthcare 1st Edition

Blass
https://ebookname.com/product/role-of-poly-vinyl-chloride-in-
healthcare-1st-edition-blass/
Bakemonogatari Part 1 Monster Tale Nisioisin
https://ebookname.com/product/bakemonogatari-part-1-monster-tale-
nisioisin/
The Chemistry of Hydroxylamines Oximes and Hydroxamic
Acids in 2 part 1st Edition Zvi Rappoport
https://ebookname.com/product/the-chemistry-of-hydroxylamines-
oximes-and-hydroxamic-acids-in-2-part-1st-edition-zvi-rappoport/
Design of Plated Structures Eurocode 3 Design of Steel

Structures Part 1 5 Design of Plated Structures First
Edition Darko Beg
https://ebookname.com/product/design-of-plated-structures-
eurocode-3-design-of-steel-structures-part-1-5-design-of-plated-
structures-first-edition-darko-beg/
The Craft of Musical Composition Book 1 Theoretical

Part 4th Edition Paul Hindemith
https://ebookname.com/product/the-craft-of-musical-composition-
book-1-theoretical-part-4th-edition-paul-hindemith/
The Chemistry of Cyclobutanes in 2 part 1st Edition Zvi

Rappoport And Joel F. Liebman (Editors)
https://ebookname.com/product/the-chemistry-of-cyclobutanes-
in-2-part-1st-edition-zvi-rappoport-and-joel-f-liebman-editors/
The Chemistry of Heterocyclic Compounds Oxazoles

Synthesis Reactions and Spectroscopy Part B 1st Edition
David C. Palmer
https://ebookname.com/product/the-chemistry-of-heterocyclic-
compounds-oxazoles-synthesis-reactions-and-spectroscopy-
part-b-1st-edition-david-c-palmer/
Academic Press is an imprint of Elsevier
225 Wyman Street, Waltham, MA 02451, USA
525 B Street, Suite 1800, San Diego, CA 92101-4495, USA
125 London Wall, London, EC2Y 5AS, UK
The Boulevard, Langford Lane, Kidlington, Oxford OX5 1GB, UK
First edition 2015
© 2015 Elsevier Inc. All rights reserved
No part of this publication may be reproduced or transmitted in any form or by any means,
electronic or mechanical, including photocopying, recording, or any information storage and
retrieval system, without permission in writing from the publisher. Details on how to seek
permission, further information about the Publisher’s permissions policies and our
arrangements with organizations such as the Copyright Clearance Center and the Copyright
Licensing Agency, can be found at our website: www.elsevier.com/permissions.
This book and the individual contributions contained in it are protected under copyright by
the Publisher (other than as may be noted herein).
Notices
Knowledge and best practice in this field are constantly changing. As new research and
experience broaden our understanding, changes in research methods, professional practices,
or medical treatment may become necessary.
Practitioners and researchers must always rely on their own experience and knowledge in
evaluating and using any information, methods, compounds, or experiments described
herein. In using such information or methods they should be mindful of their own safety and
the safety of others, including parties for whom they have a professional responsibility.
To the fullest extent of the law, neither the Publisher nor the authors, contributors, or editors,
assume any liability for any injury and/or damage to persons or property as a matter of
products liability, negligence or otherwise, or from any use or operation of any methods,
products, instructions, or ideas contained in the material herein.
ISBN: 978-0-12-802269-6
ISSN: 0065-3055
For information on all Academic Press publications

visit our website at store.elsevier.com
CONTRIBUTORS
Joseph A.B. Abdalla

Inorganic Chemistry Laboratory, Oxford, United Kingdom
Simon Aldridge
Elisabete C.B.A. Alegria
Centro de Quı́mica Estrutural, Instituto Superior Técnico, Universidade de Lisboa, Av.
Rovisco Pais, Lisbon, and Chemical Engineering Department, ISEL, R. Conselheiro Emı́dio
Navarro, Lisboa, Portugal
Marco Baron
Dipartimento di Scienze Chimiche, Università di Padova, Padova, Italy
Andrea Biffis
Elena Fernández
Departament Quı́mica Fı́sica i Inorgànica, University Rovira i Virgili, Tarragona, Spain
Maximilian N. Kopylovich
Centro de Quı́mica Estrutural, Instituto Superior Técnico, Universidade de Lisboa,
Av. Rovisco Pais, Lisbon, Portugal
Michael Limbach
CaRLa (Catalysis Research Laboratory), Heidelberg, and BASF SE, Synthesis &
Homogeneous Catalysis, Ludwigshafen, Germany
Luı́sa M.D.R.S. Martins
Av. Rovisco Pais, Lisbon, and Chemical Engineering Department, ISEL, R. Conselheiro
Emı́dio Navarro, Lisboa, Portugal
Nuno M.R. Martins
Armando J.L. Pombeiro
Ana P.C. Ribeiro
Ian M. Riddlestone
vii
viii Contributors
Cristina Tubaro
Stephen A. Westcott
Department of Chemistry and Biochemistry, Mount Allison University, Sackville,
New Brunswick, Canada
CHAPTER ONE
Coordination and Activation of

EdH Bonds (E 5 B, Al, Ga) at
Transition Metal Centers
Ian M. Riddlestone, Joseph A.B. Abdalla, Simon Aldridge*
*Corresponding author: e-mail address: [email protected]
Contents
1. Introduction 2
2. Borane (BdH) σ-Complexes 4
2.1 σ-Complexes Featuring Tetra-Coordinate Boranes 5
2.2 σ-Complexes Featuring Tri-Coordinate Boranes 9
3. Alane (AldH) σ-Complexes 19
4. Gallane (GadH) σ-Complexes 26
5. Conclusions 31
References 32
ABBREVIATIONS
ArCl C6H3Cl2-2,6
Arf C6H3(CF3)2-3,5
cat catecholato, O2C6H4-1,2
Catf O2C6H3-1,2-F-3
cdt 1,5,9-cyclododecatriene
cht 1,3,5-cycloheptatriene
cod 1,5-cyclooctadiene
Cp cyclopentadienyl
Cp0 methylcyclopentadienyl
Cy cyclohexyl
dcype 1,2-bis(dicyclohexylphosphino)ethane
Dipp 2,6-diisopropylphenyl
hppH 1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-a]pyrimidine
i
Bu isobutyl ¼ CH2CH(CH3)2
i
Pr isopropyl ¼ CH(CH3)2
Mes mesityl ¼ 2,4,6-trimethylphenyl
NHC N-heterocyclic carbene
p-cym para-cymene ¼ 4-iPrC6H4Me
Advances in Organometallic Chemistry, Volume 63 # 2015 Elsevier Inc. 1

ISSN 0065-3055 All rights reserved.
http://dx.doi.org/10.1016/bs.adomc.2015.02.003
2 Ian M. Riddlestone et al.
pin pinacolato, OCMe2CMe2O

quin quinuclidine ¼ N(CH2CH2)3CH
tbe tertbutylethene (3,3-dimethylbutene), tBuCHCH2
t
Bu tertbutyl ¼ C(CH3)3
thf tetrahydrofuran
Mes Mes Mes Mes Mes Mes Dipp Dipp

N N N N N N N N
IMes 5-Mes 6-Mes 6-Dipp
1. INTRODUCTION
Over the last 20 years, significant research effort has been expended on
probing the mode(s) of interaction of group 13 hydrides with transition
metal centers. An initial driver for such work—notwithstanding issues relat-
ing to chemical reversibility—was potential applications of boron/nitrogen
based materials containing a high weight% of hydrogen, as hydrogen storage
materials; more recent work has focussed on such systems as building blocks
in the construction of inorganic polymers.1 Applications of alanes in hydro-
gen storage media have also received some attention,2 but in general, the
hydrides of the heavier group 13 elements have not been in the spotlight,
primarily due to their lower percentages by weight of hydrogen and their
greater thermal instability.3
Control of dihydrogen release or of polymer formation, for example,
means that a significant part of this effort has been directed toward metal-
mediated processes; the interaction of EdH bonds with transition metal
centers and their potential modes of activation are therefore of key impor-
tance.4,5 As a consequence, the factors underpinning the fundamental bond-
ing interactions (σ-donation, π-acceptance) of BdH, and to a lesser extent
AldH and GadH bonds, with transition metals have been explored
(Fig. 1). The resulting data offer comparison with much more widely
established families of σ-complex, featuring coordinated HdH, CdH,
or SidH bonds.6–8
Even leaving aside complexes containing anionic borohydride-type
ligands,9 the coordination of BdH bonds at transition metal centers is well
precedented, and many BdH σ-complexes featuring three- and four-
coordinate boranes have been reported.5 Examples abound involving either
Coordination and Activation of EdH Bonds 3
ERn ERn
LxM LxM
H H
Donation from filled Back-bonding into EJH

EJH σ-bonding orbital σ∗ antibonding orbital
ERn
LxM ERn Lx M
H H
More ⬙side-on⬙ alignment allows

for greater π back-bonding
Figure 1 Key σ-donor/π-acceptor interactions in EdH σ-complexes.
κ1 or κ2 binding—that is featuring interactions with the metal center

through one or two BdH bonds, respectively. Within this sphere, there
has been a wealth of investigation into the interaction of the BdH bonds
in amine- and aminoboranes with transition metals, with such σ-complexes
having been postulated as intermediates in BdN dehydrocoupling reac-
tions.1,4 In-depth mechanistic details of such processes are not the focus
of this chapter and will not be examined in depth beyond consideration
of the modes of ligation of relevant species. Activation of one BdH bond,
generally involving oxidative addition at a metal center, is very well
established, in part reflecting the implication of such a step in a number
of processes leading to the borylation of both saturated and unsaturated
hydrocarbons.10,11 However, activation of two BdH bonds, leading ulti-
mately to dehydrogenation and the formation of a subvalent borylene com-
plex, is much less common.12,13
The related chemistry of the heaver group 13 elements aluminium and
gallium is much less developed than that of boron.14,15 The interaction of
AldH bonds with transition metal centers is limited to the formation of
a relatively small number of σ-complexes featuring bridging MdHdAl
motifs, with no reported propensity toward oxidative addition of AldH
bonds or dehydrogenation at a transition metal center.16 σ-Alane complexes
themselves are rare; the first example of an unsupported AldH σ-complex,
(cdt)Ni[κ1-HAlMe2quin], was reported by Pörschke and coworkers in
1990.14 There is an even greater paucity of examples of GadH coordination
at transition metals, in part due to the much greater thermal fragility of
GadH bonds.3 Ueno reported the first structurally characterized examples
of GadH σ-complexes, involving coordination of the amine-stabilized
gallane quinGaH3 at [Cp0 Mn(CO)2] and [M(CO)5] fragments (M ¼ Cr,
Mo, W).15 However, with the +1 oxidation state more readily accessible
for gallium (and the GadH bond being inherently weaker than its lighter
congeners),3,17 the potential for novel and interesting chemistry initiated
by the dehydrogenation of Ga(III) hydride complexes at transition metal
centers is not only foreseeable but beginning to be realized in practice.15,18
This chapter will primarily focus on reviewing the coordination and
activation of AldH and GadH bonds at transition metal centers, making
reference to key examples of related BdH σ-complexes in order to put fun-
damental issues of electronic structure and bonding into appropriate context.
In the interests of space, and with a view to comparing the intrinsic elec-
tronic/geometric properties of the coordinated σ-bond, “tethered” systems
in which the coordinated EdH bond forms part of an existing metal-bound
ligand are not as a rule included.
2. BORANE (BdH) σ-COMPLEXES

The long-standing desire to use an organometallic system to selec-
tively functionalize CdH bonds,19 and the inherent challenges related to
this process, have seen the development of a number of systems to model
the CdH bond activation process (involving, for example, silanes and
boranes as alkane mimics).5,8 The isoelectronic relationship between CH4
and [BH4] led to much interest in the formation of transition metal, lan-
thanide, and actinide borohydride complexes featuring κ1, κ2, and κ3 coor-
dination modes (Fig. 2).9,20 Although isoelectronic with CH4, the inherent
negative charge possessed by the [BH4] anion provides a significant elec-
trostatic contribution to bonding.9 Consequently, the coordination chem-
istry of neutral boranes is perceived as a better potential model for alkane
coordination, and this area has been the subject of significant interest in
the recent chemical literature. Two distinct classes of borane coordination
complex have emerged, involving three- and four-coordinate boranes,
respectively.
The formation of Lewis-base adducts of BH3 is well established, and
being charge neutral, LBH3 systems perhaps more closely resemble
alkanes in their potential ligating properties, than does the borohydride
H H
H H
LnM H B LnM B LnM H B H
H H H
H H

Figure 2 Coordination modes of BH4 at a single transition metal center.
anion. Of key importance in rationalizing the bonding in complexes con-

taining LBH3 ligands is the coordinative saturation of the boron center,
and crucially the population of the vacant boron pz-orbital by the Lewis base
(L). Consequently, the LBH3 moiety has a limited role as a π-acceptor, as
the BdH σ*-orbital is typically too high in energy to interact significantly
with metal-based d-orbitals.21 By contrast, three-coordinate boranes, arche-
typally represented by HBcat, possess a formally vacant pz-orbital at the
boron center, which is potentially of suitable energy to interact with tran-
sition metal d-orbitals allowing for π back-bonding.22,23
2.1 σ-Complexes Featuring Tetra-Coordinate Boranes

The isoelectronic relationship between neutral LBH3 adducts and alkanes
means that they offer model systems for the study of CdH activation param-
eters. A number of σ-complexes of such adducts have been reported featur-
ing a variety of Lewis bases, L. κ1-Complexes bound through a single BdH
bond can be formed via the in situ generation of a 16-electron transition
metal fragment, for example, following photolytic ejection of a CO ligand.
Accordingly, the groups of Shimoi and, more recently, Braunschweig have
synthesized a number of Group 6 metal σ-borane complexes of the type
M(CO)5(κ1-H3BL) via this route (Scheme 1).21,24
Structural characterization of these systems by single-crystal X-ray dif-
fraction shows that in each case, the borane exhibits a significantly more
“end on” binding motif than that seen in σ-silane and dihydrogen systems.6,8
This binding motif is consistent with the BdH σ-bond acting primarily as a
σ-donor with essentially negligible π-acceptor capabilities. The coordinated
BdH bond thus shows very little activation, and the complex therefore rep-
resents minimal progression along the oxidative addition pathway. Rapid
L
H
H B
CO hu
OC CO L˙BH3 H
M
OC CO −CO OC CO
M
CO
OC CO
CO
M = Cr; L = PMe3 1, PPh3 2, NMe3 3, IMe 4
M = W; L = PMe3 5, PPh3 6, NMe3 7, IMe 8
Scheme 1 Photolytic generation of four-coordinate borane σ-complexes of chromium
and tungsten.21,24
exchange of bridging and terminal BdH bonds typically results in a statis-

tically averaged 1H NMR chemical shift with the associated fluxional pro-
cess unable to be frozen out for 1–8, even at 80 °C.21
A convenient bonding comparison between LBH3 and silane
σ-complexes can also be drawn from systems featuring the [CpMn(CO)2]
fragment, again reported by Shimoi and by Braunschweig
(Scheme 2).24,25 The structures of borane complexes 9–11 (determined
by X-ray diffraction) are also consistent with the coordinated BdH bond
acting almost exclusively as a σ-donor. As such, the measured MdHdB
angles [e.g., 142(3)° for 9] are wide, and the Mn B separations are signif-
icantly longer than those found in related silane complexes [e.g., 2.682(3) Å
for 9 cf. 2.391(12) Å for Cp0 Mn(CO)2(H2SiPh2)].25,26 In addition, the ori-
entation of the coordinated BdH bond deviates significantly from the
close-to-horizontal orientation observed in silane σ-complexes in which
back-bonding from the metal-based HOMO is significant (Fig. 3).25
This close-to-vertical orientation of the BdH bonds in 9–11 attests to
negligible π-contributions to binding in each case, since the highest-lying
orbital of the 16-electron [CpMn(CO)2] fragment of suitable symmetry
for π back-bonding lies essentially coplanar with the Cp ring.27 As a conse-
quence, the infrared-measured stretching frequencies for the CO ligands are
hu
L˙BH3 H
Mn Mn H
−CO
OC CO OC H B
OC OC
L
L = NMe3 9, PMe3 10, IMe 11
Scheme 2 Photolytic generation of complexes of the type CpMn(CO)2{κ1-H3BL}.24,25
OC CO
ERn
Mn Mn Mn
H ERn
OC CO OC CO H
H
ERn
Figure 3 Schematic diagram showing limiting torsional alignments of the EdH bond in
half-sandwich sigma complexes: (left) vertical orientation, (center) horizontal orienta-
tion, and (right) overlap of HOMO of a 16-electron [CpM(CO)2] fragment with EdH
σ*-orbital in horizontal alignment.
significantly lower than those found, for example, in the corresponding

complex of the much better π-acceptor H2 [e.g., 1927/1820, 1918/1839,
and 1986/1922 cm1 for 9, 10, and CpMn(CO)2(H2), respectively].15b,25
The dominant role of σ-donation implies that complex stability is strongly
influenced by the energy match between the BdH σ-bonding orbital and
the LUMO of the transition metal fragment. Thus, the elevation of the for-
mer (e.g., by the use of more strongly σ-donating Lewis bases, L) and/or the
stabilization of the latter (e.g., by the use of a cationic metal center) would be
expected to lead to higher binding affinities for the LBH3 ligand. Thus,
Shimoi and coworkers have also reported on use of the half-sandwich ruthe-
nium chlorides CpRu(PMe3)2Cl and Cp*Ru(PMe3)2Cl as sources of cat-
ionic transition metal centers via halide abstraction, and their ability to
coordinate boranes of the type Me3EBH3 (E ¼ P or N) (Scheme 3). These
complexes feature more elongated BdH bonds than the corresponding
neutral manganese systems, an observation which is thought to reflect the
polarization of the BdH bond brought about by coordination to the more
electrophilic positively charged ruthenium center.28 The minor extent of
back-bonding is confirmed by relatively long Ru B contacts, with the
closer approach of the borane ligand in 13 [d(RudB) ¼ 2.586(5) Å vs.
2.648(3) Å for 12] presumably reflecting the enhanced donor capabilities
of the phosphine (vs. amine) donor at L.28
Stronger binding of the borane ligand might also be envisaged by the
adoption of a κ2 mode of binding, and therefore by employing a metal frag-
ment with an electron count of 14 (or lower). A number of such systems
have been reported, primarily featuring group 9 metal fragments of the types
[L2M(H)2]+ and [L2M]+ (M ¼ Rh, Ir; e.g., 16, 17, Scheme 4).13a,29,30 Much
of this work has focussed on amine borane complexes due to their potential
relevance in the catalytic dehydrocoupling of ammonia borane and related
amine-containing systems.1 While model complexes featuring tertiary
amine boranes (chiefly H3BNMe3) have been used to probe issues of
R5 R5
H
H [BAr f4]
Na[BAr f4]
Ru Ru B
Me3P Cl −NaCl Me3P H EMe3
Me3P Me3P
R = H; E = N 12, P 13
R = Me; E = N 14, P 15
Scheme 3 Formation of cationic κ1-H3BL complexes by halide abstraction.28
F NMe
H3B.NMe3 3
iPr
3P H
Rh Rh B
−C6H5F i
iPr
3P
PiPr3 Pr3P H
H
16
PiPr3 PiPr3 NMe3

H L H3B.NMe3 H H
Rh Rh B
H L H H
1,2-C6H4F2 H
PiPr3 PiPr3
L = agostic/solvent interaction 17
Scheme 4 Syntheses of group 9 metal complexes featuring κ2 amine borane ligands.29a,b
H3B.NtBuH2
IMes IMes NtBuH2 IMes
Na[BArf4] 48 h
t
Bu
H H H H H
Rh Cl Rh B Rh B N
H H H H H
C6H5F H −H2 H
IMes IMes IMes
6h
18 19
H Me
PCy3 NMeH2
PCy3 H N NMeH2
H H H H2
Ir B Ir B B
H H H H2
H H3B.NMeH2 PCy3 H H
PCy3 H H
20 −H2
Me NMeH2 −H2
H
PCy3 N
B
H H
Ir B H
H H H
H
PCy3
21
Scheme 5 Dehydrogenation of secondary amine boranes at group 9 metal centers
leading to the formation of a coordinated aminoborane (upper)13a or a linear borazane
chain (lower).29e
electronic and geometric structure, systems featuring NdH bonds are

additionally amenable to dehydrogenation—a process which has been
found to be facile at a range of transition metal centers (Scheme 5).
In particular, a number of borane complexes thought to be likely interme-
diates in metal-catalyzed dehydrogenation/dehydrocoupling have been
isolated and characterized. Weller and coworkers, for example, have inves-
tigated the dehydropolymerization of methylamine borane, H3BNMeH2,
showing that the growth of a linear borazane chain can occur by a
dehydrogenation reaction occurring between the H3BNMeH2 monomer

and the κ2-aminoborane complex [(Cy3P)2Ir(H)2(κ2-H3BNMeH2)]+
(20). This dehydrocoupling process yields [(Cy3P)2Ir(H)2(κ2-
H3BNMeHBH2NMe2H)]+ (21), which can be synthesized independently
from H3BNMeHBH2NMe2H and [(Cy3P)2Ir(H)2(H2)2]+ (Scheme 5).29e
A number of systems featuring H3BNR2X fragments bound in this fash-
ion have been characterized by X-ray crystallography: predictably, the κ2
mode of coordination brings the metal and boron centers into closer prox-
imity than is observed for κ1 complexes. Thus, for example, even allowing
for the differing radii of Rh(III) and Ru(II), the M B distance measured
for [(IMes)2Rh(H)2(κ2-H3BNMe3)]+ [23, 2.327(3) Å] is markedly shorter
than that found in [CpRu(PMe3)2(κ1-H3BNMe3)]+ [12, 2.648(3)
Å].13a,28 Given the relatively high-lying nature of the BdH σ*-orbital in
H3BNMe3, such differences presumably reflect the geometric constraints
of the four-membered M(μ-H)2B bridge, rather than any underlying elec-
tronic factors (similar effects having previously been reported for κ1 and κ2
borohydride complexes).9 Definitive determination of hydrogen atom posi-
tions in amine borane complexes by neutron diffraction techniques has been
less readily forthcoming. Very recently however, the neutron structure of
the iridium cation [Ir(5-Mes)2(H)2(κ2-H3BNHMe2)]+ (24, as the [BArf4]
salt) has been reported.30j The Ir B distance [2.21(4) Å] and Ir BdN
angle [125(2)°] determined from the heavy-atom skeleton are in line with
previous literature reports on related κ2 amine borane coordination13; in
addition, the structure reveals an essentially planar Ir(μ-H)2B ring and IrdH
and BdH distances of 1.75(7)/1.87(6) and 1.21(6)/1.29(8) Å, respectively.
The latter can be contextualized by the corresponding terminal BdH dis-
tance of 1.13(6) Å.
2.2 σ-Complexes Featuring Tri-Coordinate Boranes

Mechanistic investigations by Hartwig and coworkers into Cp2TiMe2-
catalyzed hydroboration led to the isolation of the first σ-complex of a
tri-coordinate borane.22,23 Thus, the reaction of dimethyltitanocene with
three equivalents of HBcat yields the thermally fragile bis-borane complex
Cp2Ti(κ1-HBcat)2 (25) together with methane and MeBCat (Scheme 6).
Characterization by 11B NMR spectroscopy is consistent with an appre-
ciable Ti B interaction in these systems (e.g., δB ¼ 45 ppm for 25 cf.
28 ppm for free HBcat), while the IR-measured BdH stretching frequen-
cies (e.g., 1611 cm1 for 25, cf. 2660 cm1 for free HBcat) suggest
H
Me 3 HBcat Cp2Ti(PMe3)2 PMe3
Bcat
Ti Ti Ti
Bcat Bcat
Me −MeBcat
−MeH H H
25 26
1
Scheme 6 Synthesis of Cp2Ti(κ -HBcat)2 (25) from Cp2TiMe2 and conversion
Cp2Ti(PMe3)(κ1-HBcat) (26) via ligand redistribution with Cp2Ti(PMe3)2.23,31
significant activation of the BdH bond. The solid-state structure of 25

shows that the boron atom lies in a plane which also contains both catechol
oxygen atoms and the titanium center, with the hydride (located in the dif-
ference map) sitting above this plane.23 The Ti B separation [2.335(5) Å] is
longer than those found in related metallocene boryl complexes,10a but con-
sistent with a structurally significant interaction between the two atoms. As
such, a model of bonding is proposed based on σ-donation from the BdH
bonding orbital, and back-bonding into the formally vacant boron-centered
pz-orbital. A related mono-borane complex Cp2Ti(PMe3)(κ1-HBCat) (26)
could also be prepared via a ligand redistribution reaction between Cp2Ti
(PMe3)2 and 25, and a solid-state structure determined for the closely related
fluorocatechol derivative Cp2Ti(PMe3)(κ1-HBcatf) (27).31 The BdH bond
in 27 appears to be further along the oxidative addition pathway in compar-
ison to the bis-borane 25, as reflected in the relative BdH and TidH bond
lengths [27: TidH 1.61(5) Å, BdH 1.35(5) Å; 25: TidH 1.74(4) Å, BdH
1.25(3) Å]. The greater extent of activation can be understood in terms of
the greater electron-donating capabilities of the phosphine coligand, as
well as slightly enhanced electrophilicity of the borane due to fluorine
incorporation.
Hartwig and coworkers have also investigated three-coordinate σ-borane
complexes which provide close comparison with archetypal manganese
silane σ-complexes.8,32,33 Thus, the synthesis of a range of σ-borane com-
plexes featuring the [Cp0 Mn(CO)2] fragment has also led to an understanding
of the effects of the borane substituents on the progression toward BdH
oxidative addition. Of the complexes reported, Cp0 Mn(CO)2(κ1-HBcat)
(28), Cp0 Mn(CO)2(κ1-HBpin) (29), and Cp0 Mn(CO)2(κ1-HBCy2) (30),32
28 and 29 can be synthesized via the photolytic reaction of Cp0 Mn(CO)3
with the respective borane. Substantially increased yields are obtained by
using the salt metathesis reaction between K[Cp0 Mn(CO)2H] and the
corresponding chloroborane (Scheme 7). This route proves to be particularly

apposite in the formation of 30, since the photolytic reaction of Cp0 Mn(CO)3
with HBCy2 does not proceed, presumably due to the dimeric nature of the
parent borane.
The solid-state structures of 28–30 show that the center of the BdH
bond remains essentially equidistant from the manganese center in all three
complexes, and that the oxidative addition process is reflected in a
“pivoting” around this point, the extent of which determines the MndB
and MndH distances. Of the three boranes, HBcat gives rise to the most
“side-on” binding, bearing closest resemblance to that of dihydrogen,
whereas HBCy2 is more “end on” and more closely resembles the binding
observed in Lewis base adducts of tetra-coordinate boranes LBH3 (Fig. 4).
The HBpin complex lies between those of HBcat and HBCy2. The struc-
tural data show that the π-acceptor capability of the boranes follows the
order HBcat > HBpin > HBCy2, and that the reverse trend exists for their
σ-donating capabilities.32 As seen with other families of EdH σ-complex,
the incorporation of electron-withdrawing substituents (e.g., alkoxy or
aryloxy groups) makes the LUMO of the borane ligand a better energy
match to the HOMO of the transition metal fragment, thereby enhancing
π back-bonding.8 Consequently, a shorter Mn B interaction is observed
R2BX
Mn H
Mn
OC H - KX OC
OC OC R 2B
R2 = cat 28, pin 29, Cy2 30

Scheme 7 Formation of manganese σ-borane complexes by salt metathesis.32
Mn
HBcat (28)
HBpin (29)
H
HBCy2 (30)
B
Figure 4 Overlaid positions of Mn, B, and H atoms from the crystal structures of 28–30.
Adapted with permission from J. Am. Chem. Soc. 122 (2000) 9435–9443. Copyright (2000)
American Chemical Society.
for the catechol (aryloxy) borane than pinacol (alkoxy) borane, and
dicyclohexylborane has the longest Mn B separation.
The differences in the σ-donor and π-acceptor capabilities of the three
boranes are also reflected in the infrared stretching frequencies of the CO
ancillary ligands in 28–30, with the frequencies for the HBCy2 complex
(30) being lower than those for both the HBpin (29) and HBcat (28) com-
plexes (30: 1967/1901 cm1; 29: 1981/1924 cm1; 28: 1995/1937 cm1).
As such, these data reflect a sequentially more electron-rich metal fragment
resulting from a combination of stronger σ-donation and weaker π-acceptor
properties for HBCy2 over HBpin over HBcat.32
The coordination of three-coordinate boranes at 14-electron metal
centers through two BdH bonds has also been reported, with the first
example being characterized by Sabo-Etienne and coworkers.34 The reac-
tion of Ru(H2)2(H)2(PCy3)2 with H2BMes results in the displacement of
the two dihydrogen ligands and the formation of the κ2-complex
(Cy3P)2(H)2Ru(κ2-H2BMes) (31) (Scheme 8). The Ru–B distance deter-
mined for 31 in the solid state is exceptionally short [1.938(4) Å], due—at
least in part—to the geminal bis(BdH) coordination mode. Nonetheless,
such a geometry appears better preorganized for population of the boron
pz-orbital through π back-donation than does that seen in κ1-complexes,
a supposition backed up by computational studies.
Stradiotto and coworkers have demonstrated a similar coordination
mode for H2BMes using the 16-electron precursor Cp*Ru(Cl)(PiPr3) to
generate chloroborohydride complex 32, with subsequent halide abstraction
giving a cationic system [Cp*Ru(PiPr3)(κ2-H2BMes)]+ (33) featuring κ2-
coordination of H2BMes in accordance with an 18-electron count
(Scheme 9).35 Here too, the Ru B distance is short [1.921(2) Å] and
the RuBdC angle almost linear [172.2(2)°], and DFT calculations also
show the population of the formally vacant boron-centered p-orbital as a
result of π back-donation from ruthenium.
PCy3 PCy3
H H2 H2BMes H H
Ru Ru B Mes
H H2 - 2H2 H H
PCy3 PCy3
31
Scheme 8 Displacement of two dihydrogen ligands by the borane H2BMes to form
κ2-complex 31.34
Me5 Me5 Me5
H2BMes Li[BArf4]
Ru Ru H Ru H
iPr P Cl i iPr
3 Pr3P
Mes - LiCl 3P
H B H B
Mes
32 Cl 33
Scheme 9 Formation of [Cp*Ru(PiPr3){κ2-H2BMes}][BArf4] (33). Counterion omitted for
clarity.35
With much interest being focussed on the catalytic dehydrogenation of

ammonia/amine boranes, the chemistry of their dehydrogenated counter-
parts, aminoboranes (H2BNRR0 ), has received concerted attention. Interest
in developing catalysts for the efficient release of hydrogen from ammonia/
amine boranes has meant that transition metal systems have featured prom-
inently in the literature,1,29 and the interaction of aminoboranes with
catalytically relevant transition metal centers therefore represents an area
of research relevant to both hydrogen storage chemistry and inorganic poly-
mer formation.
The aminoborane monomer is formally isoelectronic with an alkene
and therefore has the potential not only to bind through the BdH bonds
but also in an analogous manner to an alkene through the BdN
π-system.13a,30c,g,j,36,37 Sabo-Etienne and coworkers have used the
[(Cy3P)2Ru(H)2] fragment to trap a number of aminoboranes (resulting
from dehydrogenation of the parent amine boranes) as κ2-complexes.
The structure of (Cy3P)2Ru(H)2(κ2-H2BNH2) (34) shows that the parent
aminoborane H2BNH2 binds through both BdH bonds.36a Calculations
to determine the difference in energy between this mode of coordination
and the classical “side-on” binding showed the bis(σ-BH) motif to be at least
14 kcal mol1 more stable than binding through the BdN π-system. Elec-
tronic divergence from alkene donors, notably the more hydridic nature of
the BdH bonds (cf. CdH) and the lower-lying nature of the B]N π
system,38 presumably contributes to these findings. Independently, Aldridge
and coworkers observed the bis(σ-BH) binding motif for a number of
aminoborane complexes involving carbene-stabilized rhodium and iridium
cations (35–38, Fig. 5).13,30c
The groups of Weller and Sabo-Etienne subsequently prepared the
related and isoelectronic aminoborane complexes (Cy3P)2Ru(H)2(κ2-
H2BNiPr2) (39) and [(Cy3P)2M(H)2(κ2-H2BNiPr2)]+ (M ¼ Rh 40, or Ir
41).36c These complexes provide a useful platform on which to study the
PCy3 IMes
H H H R
H H
Ru B N M B N
H H H H
H R
PCy3 IMes
M = Rh; R = iPr 35, Cy 36
34
M = Ir; R = iPr 37, Cy 38
Figure 5 Initially reported κ2-aminoborane complexes. Counterions omitted for
clarity.13,30c,36a
impact of the metal fragment on the electronic/geometric structures of

aminoborane complexes. All three complexes feature the bis(σ-BH) coor-
dination mode, with back-bonding into the BdN π*-orbital (the LUMO
of the aminoborane ligand) also conceivable. The results of NBO analyses
indicate that the extent of this π back-donation decreases in the order
Ru(II) > Ir(III) > Rh(III). Greatest interaction is observed with the neutral
ruthenium complex 39, with the lower energy orbitals associated with the
cationic group 9 fragments resulting in less effective overlap with the BdN
π*-orbital. The greater radial extension of the 5d-orbitals in Ir(III) partially
compensates for this and results in greater π back-donation than in Rh(III).
While the observation of the bis(σ-BH) coordination of aminoboranes is
therefore well precedented,13a,30c,g,j,36,37 it should be noted that these sys-
tems universally feature a 14-electron transition metal center, which pre-
sumably distorts the potential energy landscape toward the adoption of
the (4-electron donor) κ2-coordination mode. Investigation of the intrinsic
ligating properties of aminoboranes as 2-electron donors (e.g., mono-BH
σ-coordination vs. BN π-bonding, for example) has therefore been carried
out using 16-electron fragments of the type [CpRu(PR3)2]+ (PR3 ¼ PPh3 or
1/2dcpe).39 The resulting complexes of H2BNCy2 uniformly feature the
aminoborane acting as a 2-electron donor through the coordination of a sin-
gle BdH σ-bond (Scheme 10).
Two fluxional processes have been shown by VT-NMR to operate in
both [CpRu(PPh3)2(κ1-H2BNCy2)][BArf4] (42) and [CpRu(dcpe)2(κ1-
H2BNCy2)][BArf4] (43) involving (i) rotation about the Rud(BH) centroid
vector; and (ii) interconversion between bound and unbound BdH bonds,
with the latter having an intrinsically higher activation barrier. It is also clear
that π back-donation provides a chemically significant contribution to
bonding. Thus, the more electron-rich complex 43 is notably more stable
Na[BArf4]/N2
H
then H2BNCy2 Ru
B
R3P H Cy
Ru Cl N
- NaCl R3P
R3P
R3P Cy
PR3 = PPh3 42,
1/2 dcpe 43
Scheme 10 Formation of κ1-aminoborane complexes of the type [CpRu(PR3)2{κ1-
H2BNCy2}]+. Counterion omitted for clarity.39
i i i
Pr3P Pr3P Me Pr3P Me
H
Me H B N
H H Cl N Cl
B
Ru B N Ru Me Os Me
H H H H
Me H H
i i i
Pr3P Pr3P Pr3P
44 45 46
Figure 6 Differing degrees of BdH bond activation in group 8 complexes containing
the H2BNMe2 fragment.36b,e
than 42, a finding consistent with the DFT calculated binding energies for
the aminoborane ligand at the two metal fragments (43: 26 kcal mol1; 42:
15 kcal mol1).39
BdH bond activation in aminoborane complexes has been shown in an
elegant study from Sabo-Etienne and coworkers to be intrinsically linked to
the extent of back-bonding from the metal fragment.36e Thus, a series of
group 8 metal complexes (44–46, Fig. 6) have been characterized which fea-
tures sequentially: a symmetrically bound H2BNMe2 ligand at Ru(II) (44),
an unsymmetrically bound ligand featuring appreciable activation of one
BdH bond (45), and an Os(IV) center bound to distinct hydride and
(α-agostic) primary boryl ligands (46). The latter description, while consis-
tent with the expectation of greater oxidative activation at the 5d metal,
contrasts with the borinium formulation originally proposed by Estereulas
and coworkers for this system.36b Formal BdH oxidative addition (as pro-
posed in 46) is a very widespread fundamental mode of reactivity, being con-
firmed as a pathway for the construction of direct MdB bonds as long ago as
1990,40 and being implicated in a number of metal-catalyzed processes
for the borylation of organic substrates.10,11 As such, its complete coverage
is beyond the scope of this chapter, and only selected examples of BdH
activation are examined here.
iPr
IMes IMes 3P
H H Me H H
Ir B N Rh Cl Rh
Me
H H Me B N B(OR)2
Me iPr P
IMes IMes 3
H
47 48 (OR)2 = cat 49,
pin 50
Figure 7 Varying degrees of BdH bond activation in group 9 borane complexes.
Counterions omitted for clarity.41a,36f
Related to systems 44–46 are cationic group 9 complexes formed by

dehydrogenation of dimethylamineborane, H3BNMe2H, and featuring
markedly different degrees of activation of the boron-containing ligand
(47 and 48; Fig. 7).36f Thus, the 18-electron iridium complex [(IMes)2Ir
(H)2(κ2-H2BNMe2)]+ (47) can be viewed as a straightforward κ2 adduct
of the aminoborane dehydrogenation product, while the 14-electron rho-
dium species [Rh(IMes)2(H)(B(H)NMe2)]+ (48) (which results from
formal loss of a second equivalent of dihydrogen) is formulated as a rho-
dium aminoboryl hydride, analogous to 46. The bent RhdBdN frame-
work [132.6(10)°], short RhdB bond (1.960(9) Å cf. 2.204(4) Å for
[(IMes)2Rh(H)2(κ2-H2BNiPr2)]+),13 and RhdH/BdH locations deter-
mined by single-crystal neutron diffraction measurements for 48 provide
strong evidence for effectively complete BdH bond cleavage.36f Thus,
the metal-bound hydrogen atom is characterized (in the solid state) by sep-
arations of 2.53(3) Å (to boron) and 1.40(2) Å (to rhodium). These can be
compared with the analogous distances measured by Marder and coworkers
(also by neutron diffraction) for Rh(PiPr3)2H(Cl)Bcat (49) and Rh(PiPr3)2H
(Cl)Bpin (50) [RhdH: 2.004(10) and 2.013(5) Å; BdH: 1.53(1) and 1.57
(1) Å, respectively]—compounds that are thought to possess “modest” resid-
ual BdH interactions.41a The degree of activation of the BdH bond in 48
can be further put in context when compared with the half-sandwich rho-
dium systems reported by Hartwig and coworkers. Thus, the short BdH
contacts determined in Cp*Rh(Bpin)2(H)2 (51) and Cp*Rh(Bpin)3(H) (52)
(<1.70 Å), for example, are indicative of the retention of structurally (and
chemically) more significant BdH interactions, an assertion given further
weight by computational studies.42
While oxidative cleavage of a single borane BdH bond at a transition
metal center is well established, activation of two BdH bonds at the same
metal center, leading to dehydrogenation and the formation of a subvalent

borylene complex, is much less common. The only example of such a
process occurring spontaneously involves the reaction of MesBH2 with
(Cy3P)2Ru(H)(H2)Cl, yielding the κ2 complex (Cy3P)2Ru(H)(Cl)(κ2-
H2BMes) (53) which loses H2 under vacuum to form the borylene complex
(Cy3P)2(Cl)(H)Ru(]BMes) (54; Scheme 11).12 This remarkable process is
reversible and is shown to be accompanied by a very stark contraction in the
MdB distance [e.g., 1.780(4) Å for 54 cf. 1.938(4) Å for (Cy3P)2(H)2Ru(κ2-
H2BMes), 31], although the position of the metal-bound hydrogen atom in
54 could not be established crystallographically.
Similar dehydrogenation processes can be effected for aminoborane
complexes (Scheme 12), although, in both cases, the use of the dihydrogen
acceptor tertbutyl ethene (tbe) is required to drive the formation of the
unsaturated boron-containing ligand, and the process is therefore invariably
irreversible. In the case of [(p-cym)Ru(PCy3)(H)(]BNiPr2)]+ (55, as the
[BAr 4f ] salt)—formulated as a (hydrido)ruthenium κ1-aminoborane
PCy3 PCy3 vacuum PCy3

H H H H -H2 H
MesBH2
Ru Ru B Mes Cl Ru
Cl Cl BMes
H H
PCy3 PCy3 PCy3
53 54
Scheme 11 Reversible dehydrogenation of mesitylborane at Ru(II) leading to the for-
mation of borylene complex (Cy3P)2(Cl)(H)Ru(]BMes) (54).12
i iBu i
Pr Pr
iPr
H
iPr
Ru Ru
N B
Cy3P B iPr iBu Cy3P N
H _ H iPr
H
55 56
IMes IMes
H H Cy tBu H
Ir B N Ir B
Me H Cy Me N C
y
Cy
Mes tBu Mes
N N N N
_
Me Me
57 58
Scheme 12 Dehydrogenation of aminoborane complexes by the use of tbe as a sacri-
ficial dihydrogen acceptor. Counterions omitted for clarity.13a,c
complex—dehydrogenation generates [(p-cym)Ru(PCy3)(H)(]BNiPr2)]

[BAr 4f ] (56) which features a linear RudBdN unit and a 11B NMR shift
(δB ¼ 77 ppm) in the region expected for a terminal aminoborylene com-
plex.13c,10d Interaction of the boron center with the metal-bound hydride
is relatively weak, as manifested by a B H contact of 1.71(6) Å. In the case
of iridium cation 58, however, despite the short IrdB distance [1.881(8) Å
cf. 1.892(3) Å for the authentic iridium aminoborylene complex Cp*Ir(CO)
{]BN(SiMe3)2}],43 noticeable bending at the boron center
[∠IrdBdN ¼ 167.2(6)°] and a relatively high-field 11B chemical shift
(δB ¼ 38 ppm) are indicative of a more significant interaction with the
metal-bound hydride. As such, 58 has been described in terms of a position
between limiting base-stabilized borylene and α-agostic boryl valence bond
descriptions (Fig. 8).13a
It is interesting to note that all three examples of borane
dehydrogenation—be it spontaneous or via the use of a sacrificial
alkene—feature a metal center bearing an additional terminal hydride
ligand. Whether this is mechanistically significant—in terms, for example,
of providing a sink for one of the initially B-bound hydrogens prior to loss
of H2/alkane—is in need of further computational enlightenment.
Experimental evidence for the viability of fundamental steps leading to
borane dehydrogenation has been obtained through the stepwise synthesis of
[mer-(Me3P)3Ir(H)2(]BNCy2)]+ (60, Scheme 13). Thus, subsequent to
simple BdH oxidative addition at Ir(I), B-to-M α-hydrogen migration
H H
M BNCy2 M BNCy2
Base-stabilized α-Agostic
borylene complex boryl complex
Figure 8 Limiting valence bond descriptions of 58.13a
PMe PMe3
3
H R PMe3 H f H R
Ir(PMe3)3Cl(coe) Na[BAr 4]
B N Cl Ir B Me3P Ir B N
-coe -NaCl
H R Me3P N R Me3P R
H H
R
59 60
Scheme 13 Stepwise transfer of H2 from an aminoborane to an iridium center by
oxidative addition and B-to-M α-hydrogen migration. Counterion omitted for clarity.13b
(in this case brought about by abstraction of a chloride coligand) can be

shown to complete the formal borane dehydrogenation process.13b
3. ALANE (AldH) σ-COMPLEXES

In contrast to the large volume of literature pertaining to the interac-
tion of BdH bonds with transition metal centers, reports of AldH bond
coordination are comparatively sparse. A number of complexes featuring
the coordination of the [AlH4] and related aluminate anions to early tran-
sition metal centers have been reported.44 However, as in the case of com-
plexes of the [BH4] anion,9 the electrostatic contribution to bonding is
thought to be highly significant, and such systems are not usually considered
as “true” σ-complexes. Neutral complexes featuring unsupported AldH
bond coordination, similar to those outlined above for boranes, are notably
scarce and have been the subject only of sporadic reports in the literature.
Early work from Lobkovsky, Bulychev, and coworkers in this area
focussed on the binding of alanes at relatively hard early metal centers, in
which AldHdM-bridging interactions are typically augmented by coor-
dination of a further metal-bound ligand at aluminium. Thus, the structural
chemistry of complexes of the type (Cp2YCl)2(H3AlL) has been investi-
gated, and the effects of the Lewis base on intermolecular aggregation pro-
bed.45 The use of diethyl ether results in the formation of the polymeric
system [(Cp2YCl)2H3AlOEt2]n (61), while the stronger σ-donor NEt3
yields dimeric [(Cp2YCl)2(H3AlNEt3)]2 (62; Fig. 9). Structural character-
ization of 62 reveals secondary interactions between the bridging chloride
ligands and aluminium, which provide an additional tether to stabilize the
coordination of the AldH bond to the yttrium center.
Rosenthal and coworkers have also characterized AldH σ-complexes
which feature an additional “tether” augmenting the AldHdM interaction
H
Et3N H
Cp
Al
Cl Y Cp
H
H
Cp Y Cl
Al
Cp
H NEt3
H
Figure 9 Structure of dimeric [(Cp2YCl)2(H3AlNEt3)]2, 62.45
(Fig. 10).46 Thus, the vinylpyridine linkage in 64 acts as a bridge between the
i
Bu2AlH and zirconocene units providing intermetal connectivity in addi-
tion to the AldHdZr interaction. The same can be said for 63 in which
coordination of the AldH bond effectively constitutes an intramolecular
interaction. Alane lability has been explicitly shown to be a feature of some
complexes of this type. Thus, Cp2Zr(H)(μ-H)2[Al(H){(NDippCMe)2CH}]
(65) has been shown by Crimmin et al. to exist in solution in equilibrium
with the free alane, {HC(MeCDippN)2}AlH2, and Cp2ZrH2.47 Objective
comparison of the AldHdM bonding in these systems with classical
σ-complexes is therefore not easily accomplished, as the tether is likely to
influence both geometric and thermodynamic aspects of complexation.
Unsupported alane coordination was first reported in the work of
P€ orschke and coworkers, who exploited the quinuclidine adduct of
dimethylalane (quinAlHMe2) in the synthesis of the nickel(0) complex
(quinAlMe2H)Ni(cdt) (66) (Scheme 14).14 Remarkably, the AldHdNi
interaction remains intact upon exposure of 66 to carbon monoxide, which
results in displacement of the cdt ligand affording (quinAlMe2H)Ni(CO)3
(67). The stability of this interaction, even in the presence of CO, has been
attributed to the strongly electron-donating properties of quinuclidine and
tBu
iBu iBu
Dipp
Cp2Ti Al
H
H N H N
H H
Al Cp2 Zr Al
iBu
Cp2Zr N
H
THF H
tBu
Dipp
63 64 65
Figure 10 Group 4 alane complexes featuring additional supporting “tethers” between
aluminium and titanium/zirconium.46,47
quin·AlHMe2 N 3 CO N CO
Ni H
H
Al Ni Al Ni
- cdt
CO
Me Me
Me Me CO
66 67
Scheme 14 Formation of the first unsupported σ-alane complexes 66 and 67.14
the methyl substituents at aluminium which reduce latent Lewis acidity and
increase the σ-donor strength of the AldH bond.
An alternative—although not widely applicable—method for the forma-
tion of AldH σ-complexes is through CdH bond activation; electron-rich
transition metal complexes containing aluminium(I) donors can undergo
CdH activation across the MdAl bond. Thus, through the activation of
benzene in this manner, Fischer and coworkers have synthesized the nickel
complex (Cp*Al)3Ni{HAlPh(η2-C5Me5)} (68) (Scheme 15),48a which can
be considered to be a σ-complex featuring coordination of (η2-C5Me5)(Ph)
AlH to (Cp*Al)3Ni through an AldH bond. The activation of benzene is
presumed to go proceed via a low coordinate nickel complex of the type
[Ni(AlCp*)3], followed by a subsequent rearrangement to form 68.49a
The same group subsequently reported the formation of iron-containing
σ-alane complexes, again resulting from coordination of the Cp*Al
moiety.48b
Coordination of AldH bonds at the archetypal transition metal frag-
ments [Cp0 Mn(CO)2] and [W(CO)5] was only reported as late as 2012,49
utilizing bulky chelating N-donor-stabilized alanes (e.g., featuring
β-diketiminate or amidinate/guanidinate backbones). In line with synthetic
routes developed for σ-borane complexes, the use of either photolytic CO
substitution or salt metathesis (employing an aluminium halide precursor)
can be used to produce alane complexes containing the [Cp0 Mn(CO)2] frag-
ment (e.g., 69 and 70, Scheme 16), while CO displacement is also effective
for the synthesis of the guanidinato-alane complex W(CO)5[κ1-H2Al
{(NDipp)2CNiPr2}] from W(CO)6.49a,c
The syntheses of systems such as Cp0 Mn(CO)2[κ1-H(Cl)Al
{(NiPr)2CPh}] (69) and Cp0 Mn(CO)2[κ1-H2Al{(NDippCMe)2CH}]
(70) allow direct comparison of the binding characteristics of the AldH
bond with, for example, coordinated HdH, BdH, and SidH bonds.
AlCp*
(Cp*Al)4 H Ni
Ni(cod)2 AlCp*
C6H6 Cp*Al AlCp*
Ph
68
Scheme 15 CdH activation of benzene, leading to the formation of (Cp*Al)3Ni{HAlPh
(η2-C5Me5)}, 68.48a
iPr
iPr
Cl N K[Cp⬘Mn(CO)2H]
H
Al Ph Mn N
Al
Cl N -KCl Ph
OC CO Cl N
iPr
iPr
69
Dipp
Dipp
H N Cp⬘Mn(CO)3
H N
Al Mn
H hn Al
N
-CO OC
CO H
Dipp N
Dipp
70
Scheme 16 Salt metathesis and photolytic ligand displacement routes to manganese
complexes containing coordinated AldH bonds.49a,c
Thus, the CO stretching frequencies measured for 70 (1947 and 1879 cm1)
can be compared to analogous values of 1995–1967 and 1937–1901 cm1
for σ-complexes of tri-coordinate boranes (which possess π-acceptor capa-
bilities)32 and 1947–1919 and 1858–1820 cm1 for tetra-coordinate
boranes.24,25 These data are therefore indicative of a predominantly σ-donor
role for the {HC(MeCDippN)2}AlH2 ligand. 69, on the other hand, fea-
tures an alane ligand bound in a more “side-on” fashion, as shown geomet-
rically by (i) the reduced Mn Al distance [2.446(1) cf. 2.654(1) Å for 70
and 2.60 Å for the sum of the respective covalent radii]49,50a,c; and (ii) a sig-
nificantly narrower MndHdAl angle [97(1) vs. 109(2)° for 70]. In addi-
tion, the carbonyl stretching frequencies determined for 69 (1974 and
1899 cm1) are significantly higher than those measured for 70 (and com-
parable to those for complexes of tri-coordinate boranes), implying that
back-donation to the alane in 69 is more significant.32 Moreover, this notion
is reinforced structurally by the torsional alignment of the AldH bond,
which lies approximately perpendicular to the Cp centroid-Mn vector
(centroid-MndAldH torsion angle ¼ 105.1°), an orientation which offers
the potential for overlap between the HOMO of the [Cp0 Mn(CO)2] frag-
ment and an orbital of AldH σ* character (see Fig. 2). By means of com-
parison, the analogous torsion angle in Cp0 Mn(CO)2{(H)Si(F)Ph2} is
111.3° and that in Cp0 Mn(CO)2(HBcat) is 89.1°.26,32 Presumably, differ-

ences between 69 and 70 reflect, at least in part, the presence of the chloride
substituent at aluminium in the former, given that electronegative substitu-
ents are known in the case of silane σ-complexes to reduce the energy of the
SidH σ*-orbital and thereby augment back-bonding.8 However, while it is
tempting to ascribe geometric differences between the amidinate and
β-diketiminate systems to divergent electronic properties of the two ligands
(and potentially also to the greater steric demands of the latter), it has been
shown through quantum chemical calculations that the energetic differences
between various alignments of the AldH bond in these systems are actually
relatively small, such that they lie well within the bounds, for example, of
crystal packing forces. As such, it may well be the crystal environment, rather
than intrinsic bonding capabilities which determine the subtleties of ligand
binding, in the solid state at least.49c
DFT studies have also been used to estimate ligand binding energies: in the
case of [Cp0 Mn(CO)2] complexes, the affinity for the {HC(MeCDippN)2}
AlH2 ligand is found to be comparable to or even slightly greater than that
found for H2, but markedly less than that for CO. In addition, the relatively
similar alane binding energies calculated for [Cp0 Mn(CO)2] and [W(CO)5]
systems (cf. much larger differences for the H2 and CO complexes) are con-
sistent with the minor role of π back-bonding in alane coordination.49a
In a similar manner to its reaction with Cp0 Mn(CO)3, {HC
(MeCDippN)2}AlH2 also displaces CO from M(CO)6 (M ¼ Cr, Mo) under
photolytic conditions, although the more labile nature of the carbonyl
ligands in these hexacarbonyl systems means that a mixture of κ1- and κ2-
alane complexes (of [M(CO)5] and [M(CO)4], respectively) is generated.49d
No reaction is observed with W(CO)6 under analogous conditions. By con-
trast, more labile alkene-containing sources of the [M(CO)4] fragment, such
as M(CO)4(cod), prove to be effective for the selective (thermal) synthesis of
κ2-complexes (Scheme 17). Thus, the reaction of W(CO)4(cod) with {HC
(MeCDippN)2}AlH2 generates W(CO)4[κ2-H2Al{(NDippCMe)2CH}]
(73) (albeit at 70 °C), while the analogous reaction with Cr(CO)4(cod)
offers selective access to the corresponding κ2 chromium system
Cr(CO)4[κ2-H2Al{(NDippCMe)2CH}] (71), free from contamination
with the κ1-species inherent in the photolytic methodology.49a
A similar synthetic protocol employing Mo(CO)4(cod) can be used to
give access to related κ2-complexes featuring N-heterocyclic carbene-
stabilized AlH3 as the σ-ligand (e.g., 74 and 75, Scheme 18).49b Attempts
to extend this approach further, however, using (triene)molybdenum
Dipp Dipp
CO
H N N H
M(CO)4(cod) CO
Al Al M
H H CO
N N
CO
Dipp Dipp
M = Cr 71, Mo 72, W 73
Scheme 17 Use of M(CO)4(cod) (M ¼ Cr W) in the synthesis of κ2 complexes of
{HC(MeCDippN)2}AlH2.49a,d
N N
Ar Ar
Al Mo(CO)3(cht)
H
Mo(CO)4(cod) H 6Mes
H 2
Al
N Ar O O
C H H C
CO H
N
H CO OC Mo Mo CO
Ar Al Mo
H CO H H
H C Al C
CO O O
6Mes H
Ar = Mes 74, Dipp 75 76
Scheme 18 Reactions of NHC-stabilized alanes with sources of [Mo(CO)4] and [Mo(CO)3]
fragments.49b,d
tricarbonyl systems in an attempt to enforce κ3-alane coordination, result

instead in the formation of very sparingly soluble multimetallic systems
(e.g., 76) featuring bridging modes of coordination of the alane. DFT cal-
culations designed to probe the geometric preferences of alane coordination
at [Mo(CO)3] show that a κ3 mode of binding lies relatively high in energy
and features long ModH contacts (2.228–2.336 Å). Moreover, the related
κ2 system, featuring one fewer ModHdAl interaction lies ca.
14.4 kcal mol1 lower in energy (despite featuring a formally 16-electron
molybdenum center) presumably due in part to better overlap of Mo-
and H-centered orbitals.
Thus, using an alkene-displacement approach, a range of
β-diketiminato- and NHC-stabilized κ2-alane complexes of [M(CO)4]
(M ¼ Cr, Mo, W) fragments have been synthesized and structurally

characterized,49b,d with the general findings that: (i) the M Al distances
are similar for the two sets of compounds (e.g., 2.585(2) Å for
Mo(CO)4[κ2-H2Al{(NDippCMe)2CH}] (72) and 2.594(1) Å for 75), con-
sistent with their common κ2 mode of coordination and with the tetra-
coordinate nature of the group 13 metal center in each case; (ii) the trend
in the M Al distances as a function of M correlates well with covalent
radius for M ¼ Cr and Mo,50 but is somewhat shorter than expected in
the case of M ¼ W, presumably due to better overlap of the AldH σ-bond
manifold with the more extended 5d-orbitals of tungsten; and (iii) shorter
bonds within the [M(CO)4] fragment are observed for both sets of com-
plexes for the Md(CO) linkages trans to the AldH σ-bond, consistent with
a weak π-acceptor role for the tetra-coordinate alane ligand, be it NHC or
Nacnac supported.
Late transition metal alane σ-complexes are extremely rare: Crimmin
and coworkers have also used the {HC(MeCDippN)2}AlH2 ligand in an
attempt to address this situation and have investigated its coordination
(together with that of a related Nacnac-derived alane) at Cu(I). The κ1 mode
of coordination observed in 77 in the solid state is intrinsically very weak and
the alane rapidly exchanges with toluene at room temperature
(Scheme 19).51
While the coordination of AldH bonds is not common, activation is all
but unknown, with no unambiguous examples having been reported of
transition metal aluminyl hydride formation by AldH oxidative addition.
The activation of an AldH bond at a main group metal center, on the other
hand, has been reported, with Nikonov and coworkers exploiting Roesky’s
strongly reducing (Nacnac)Al(I) system in the cleavage of AldH (and other
EdH) bonds (Scheme 20).16,52
Among transition metal complexes, the system which is perhaps furthest
advanced along the AldH activation trajectory is the unusual cobalt system
ArCl Dipp ArCl

Dipp
N H N N H
N
Cu + Al Cu
Al
H Toluene N H
N N
N
Cl
ArCl Dipp Ar Dipp
77
Scheme 19 Reversible coordination of {HC(MeCDippN)2}AlH2 at {HC(MeCArClN)2}Cu.51
Dipp
Dipp Dipp Dipp
H N
N H N
N
Al
Al + Al
Al
H N
N N H
N
Dipp
Dipp Dipp
Dipp
78
Scheme 20 Reversible oxidative addition of an AldH bond at Al(I) to give Al(II) hydride
complex 78.16
Dipp OCCo(CO)3 Dipp OCCo(CO)

Me 3
Me
OC CO OC CO
N N
Al Co CO Al Co CO
N N
H H H
H
Me Me
Dipp Dipp
79
Figure 11 Limiting descriptions of [(OC)3Co(μ-H)2Al{(NDippCMe)2CH}][Co(CO)4], 79.49d
[(OC)3Co(μ-H)2Al{(NDippCMe)2CH}][Co(CO)4], 79 (Fig. 11). This sys-

tem, formed in the reaction of Co2(CO)8 with {HC(MeCDippN)2}AlH2,
features short CodH [1.46(3) and 1.48(3) Å] and long AldH contacts [1.98
(3) and 1.92(3) Å], with both AldHdCo units found on one side of the
CodAl vector. These observations, together with the short CodAl dis-
tance [2.330(1) Å] and computational evaluation of the various metal/ligand
fragmentation pathways, imply that a formulation in between limiting
descriptions as a κ2-alane complex of [Co(CO)3] and an alumin-diyl com-
plex of [Co(CO)3(H)2] is most appropriate.49d
4. GALLANE (GadH) σ-COMPLEXES

Given the scarcity of σ-alane complexes, it is perhaps not surprising
that the number of σ-gallane complexes is fewer still. At least in part, this
reflects the difference in reactivity and stability of AldH and GadH bonds
(e.g., mean bond dissociation energies of ca. 67 and 62 kcal mol1, respec-
tively).3,17 Although very sensitive toward moisture, the AldH bond is
thermally robust in comparison to its gallium counterpart. Thus, while
Me3NAlH3 is stable at room temperature and can be sublimed at ca. 40 °C,

Me3NGaH3 begins to decompose above 30 °C.53 The handling of gallane
itself, Ga2H6, requires specialist grease-free glassware as well as low-
temperature storage under vacuum.54 The sensitivity of gallanes therefore
represents a significant challenge in the synthesis of σ-gallane complexes.
In 1991, the thermally robust quinuclidine adduct of gallane, quinGaH3,
was reported (which decomposes only at temperatures in excess of
100 °C),55 and subsequently, the first σ-(GaH) complex was reported,
utilizing this adduct as the GadH containing ligand.15a Thus, a σ-gallane
complex of [W(CO)5] could be formed either via direct photolysis of
W(CO)6 in the presence of quinGaH3 or by the thermal displacement of
thf from W(CO)5(thf ) (Scheme 21). Although structurally characterized,
W(CO)5(κ1-H3Gaquin) (80) decomposes slowly at room temperature,
and more quickly upon heating to 70 °C. More recently, the related com-
plex Cp*Mn(CO)2(κ1-H3Gaquin) (81) was reported, allowing geometrical
parameters to be compared to classical silane and borane complexes.15b In
contrast to the complexes of the type CpMn(CO)2(κ1-H3BL), the GadH
bond is bound significantly more “side-on” and the metal–ligand interaction
appears therefore to feature a greater contribution from π back-donation
than that observed in the related LBH3 complexes 9–11. This is also implied
from the comparative MndB and MndGa distances, with the latter being
shorter in gallane complex 81 [2.567(1) vs. 2.682(3) Å for the related
κ1-(H3BNMe3) complex 9],15a,25 although still longer, for example, than
the direct (unsupported) MndGa bond found in Cp0 Mn(CO)2[Ga
{(NDippCMe)2CH}] [85, 2.311(2) Å, vide infra].18 It does appear therefore
that the gallane complex is further along the oxidative addition pathway than
CO hu thf
H
quin.GaH3 Ga quin.GaH3
OC CO OC CO
W H H W
OC CO −thf OC CO
−CO OC CO
CO W CO
OC CO
CO
80
Scheme 21 Thermal and photolytic routes to (OC)5W(κ1-H3Gaquin), 80.15a
analogous borane complexes, an assertion backed up by preliminary data

implying a much lower energy for the GadH (vs. BdH) σ*-orbital dis-
cussed in Ref. 15b.
The thermal displacement of thf from W(CO)5(thf ) in the presence of
half an equivalent of quinGaH3 results in the formation of the bridged com-
plex {W(CO)5}2(μ2:κ1,κ1-H3Gaquin) (82) featuring κ1-coordination of
the quinGaH3 to two [W(CO)5] fragments. Interestingly, 82 is reported
to react further when dissolved in thf, eliminating dihydrogen to form a for-
mal W]Ga double bond to one of the tungsten moieties, although exper-
imental details of this particular chemistry have not been published.15b The
elimination of hydrogen results in a hydridogallylene complex in which the
GadH bond is coordinated to a [W(CO)5] fragment, and the gallium center
is additionally stabilized by quinuclidine and thf donors (83, Scheme 22).
The propensity of gallane GadH bonds to undergo metal-mediated
activation is becoming increasingly apparent as the body of experimental
data pertaining to gallane coordination becomes larger. The role of the
supporting donor framework at the gallium center is clearly important in
such chemistry, however, with more electron-rich N-heterocyclic
carbene-stabilized gallanes showing essentially no propensity for GadH
activation, while amino-gallanes show a much more pronounced tendency
for dehydrogenation. Thus, a range of κ2-gallane complexes of the type
M(CO)4(κ2-H3GaNHC) (where M ¼ Cr, Mo, and NHC ¼ 6-Dipp,
6-Mes) can be synthesized from M(CO)4(cod) in a manner analogous to
the corresponding alanes and (like their aluminium counterparts) can be
shown to be inert toward loss of H2 (see Scheme 18).49d
By contrast, the reactions of the β-diketiminato-stabilized gallium
dihydride {HC(MeCDippN)2}GaH2 with a range of mono- and dinuclear
metal carbonyl reagents demonstrate, perhaps more clearly than any
other systems, the propensity for gallanes to lose dihydrogen and form
N quin
thf CO
1/2 quin·GaH3 (CO)5W −H2 OC CO OC CO
Ga H W
(thf)W(CO)5
H OC Ga W CO
W(CO)5 CO H
H OC CO
thf
82 83
Scheme 22 Formation and dehydrogenation of a bridging gallane σ-complex.15b
donor/acceptor complexes featuring the Ga(I) carbenoid ligand {HC

(MeCDippN)2}Ga.18 Thus, far from simply mimicking the chemistry of
the corresponding alane {HC(MeCDippN)2}AlH2, which yields κ1 and
κ2 AldH σ-complexes with similar reagents,49a,d the weaker nature of
GadH bonds leads to extensive dehydrogenative bond activation chemistry.
One of the most clear-cut demonstrations of the greater lability of GadH
bonds comes from the photolytic reaction of {HC(MeCDippN)2}GaH2
with Cp0 Mn(CO)3. In common with its alane counterpart, this reaction
under mild conditions generates a σ-complex, viz., Cp0 Mn(CO)2[κ1-H2Ga
{(NDippCMe)2CH}] (84). However, in contrast to the σ-alane complex,
Cp0 Mn(CO)2[κ1-H2Al{(NDippCMe)2CH}] (70), 84 is photo-labile, losing
H2 under further UV irradiation to generate the gallylene complex Cp0 Mn
(CO)2[Ga{(NDippCMe)2CH}], 85 (Scheme 23).18
From a spectroscopic viewpoint, σ-complex 84 displays two CO
stretching bands (1951/1886 cm1), similar to those reported for 70
(1947/1879 cm1), implying similar donor characteristics for the alane
and gallane ligand (a finding also reflected in the very similar geometric
structures of the two systems).18,49a The corresponding bands for 85 are
markedly red-shifted (1903/1837 cm1), however, consistent with the
stronger σ-donor capabilities of the gallylene ligand. Moreover, from a
structural perspective, the change from a κ1-gallane to gallylene donor is sig-
naled by a >12% shortening of the MndGa distance [from 2.643(2) for 84
to 2.311(2) Å for 85]. A similar tendency toward metal-mediated dehydro-
genation is observed with group 6 metal carbonyls of the type M(CO)4(cod)
(M ¼ Cr W). Thus, Cr(CO)4[κ2-H2Ga{(NDippCMe)2CH}] (86) is the
only simple κ2 adduct of the Nacnac-stabilized gallane which can be trapped,
albeit as a cocrystallite with the (dehydrogenated) gallylene system
Cr(CO)5[Ga{(NDippCMe)2CH}] (87). Reactions with Mo(CO)4(cod)
and W(CO)4(cod) by contrast exclusively generate the gallylene complexes
Dipp Me
Dipp
Me N
H hn
N
Mn Mn Ga
Ga
-H2 OC N
OC CO CO
H N Me
Dipp
Dipp
Me
84 85
Scheme 23 Manganese-mediated dehydrogenation of a gallane σ-complex.18
M(CO)5[Ga{(NDippCMe)2CH}] (and H2), with the additional carbonyl

ligand apparently being sequestered from the M(CO)4(cod) starting mate-
rial. The corresponding alane, {HC(MeCDippN)2}AlH2, on the other
hand, consistently generates robust κ2 σ-complexes of the type
M(CO)4[κ2-H2Al{(NDippCMe)2CH}] (71–73; Scheme 17) in its reactions
with M(CO)4(cod) (M ¼ Cr W).49a,d
The reactivity of {HC(MeCDippN)2}GaH2 toward homoleptic mono-
and dinuclear metal carbonyls is also characterized by loss of dihydrogen
and the formation of donor/acceptor complexes featuring the Ga(I)
carbenoid ligand {HC(MeCDippN)2}Ga. By consideration of the differing
products, Co2(CO)7Ga{(NDippCMe)2CH} (88) and (H)Mn(CO)4Ga
{(NDippCMe)2CH} (89), obtained from the reactions with Co2(CO)8
and Mn2(CO)10, two alternative dehydrogenation pathways are revealed,
with either H2 or MdH bonds acting as the ultimate hydrogen sink
(Scheme 24).18
In the case of the cobalt system 89, the reaction is thought (on the basis of
computational studies) to proceed via extremely facile GadH oxidative
addition to one metal center of the photolytically generated [Co2(CO)7]
fragment. This yields a (hydrido)cobalt gallyl complex with a single hydro-
gen atom attached to both cobalt and gallium atoms. Subsequent rotation
about the CodGa bond precedes rate-limiting loss of H2, which occurs
with a free-energy barrier of ca. 27 kcal mol1. This mechanism is very sim-
ilar to that proposed for the analogous reaction with Fe(CO)5, which gen-
erates the closely related (albeit mononuclear) iron gallylene complex
Me Dipp
N H
Ga
H
N
Mn2(CO)10 / hn Me Co2(CO)8 / hn
Dipp
-HMn(CO)5 -H2
Me Dipp Dipp
H CO Me OC CO CO
N N
Ga Mn CO Ga Co Co CO
N N
OC
Me CO Me CO OC CO
Dipp Dipp
88 89
Scheme 24 Activation of the GadH bonds in {HC(MeCDippN)2}GaH2 by Co2(CO)8 and
Mn2(CO)10.18
Fe(CO)4Ga{(NDippCMe)2CH} (90).18 In the case of Mn2(CO)10, how-

ever, the corresponding activation reaction at [Mn2(CO)9] would generate
a more sterically encumbered metal center in the initial step, and MndH
reductive elimination is presumably therefore favored over H2 loss, leading
to the observed formation of HMn(CO)5 and the monometallic manganese
gallylene complex 88.
Finally, it is of note that Himmel and coworkers have recently reported
the catalytic dehydrogenation of an amine gallane with bicyclic guanidine
ligands using an iridium-based catalyst {η3-1,3-(OPtBu2)2C6H3}IrH2.2c
Thus, H3GaNMe3 and the guanidine-stabilized gallane H3GahppH can
be dehydrocoupled using this catalyst to form [H2Ga(μ-hpp)]2 with evolu-
tion of H2. There is, however, no direct evidence for a mechanism involving
activation of the GadH bond at the iridium center directly, nor any sug-
gestion of an intermediate featuring bridging IrdHdGa interactions.
5. CONCLUSIONS
The significantly weaker nature of AldH and GadH bonds com-
pared to their borane counterparts is one of the reasons why the coordina-
tion chemistry of the heavier congeners has remained for many years
relatively underdeveloped. With the availability of alanes and gallanes fea-
turing strongly donating and/or sterically demanding substituents (such as
quinuclidine, N-heterocyclic carbenes, β-diketiminates), this situation has
begun to be addressed, and fundamental features of AldH and GadH con-
taining ligands begun to emerge. Here too, the respective EdH bond
strengths apparently play a key role in defining aspects of structure/bonding
and reactivity. Thus, coordination of four-coordinate boranes and gallanes at
[CpMn(CO)2] fragments, for example, reveals a more side-on alignment for
the latter donor, consistent with greater back-bonding into the (lower
energy) GadH σ*-orbital.15a,25 Intrinsic bond strengths might also play a
role in the markedly differing capacities of boranes, alanes, and gallanes to
undergo activation at transition metal centers. Superficially, the successively
weaker EdH bonds (ca. 89, 67, and 62 kcal mol1, respectively)3,17 might
signal a greater propensity for activation for the heavier elements. In prac-
tice, while GadH and BdH bonds are prone to activation, AldH
bonds are largely inert to oxidative addition, with one recent example
being reported utilizing a highly reducing main group metal center (and
even then giving rise to a reversible activation process).16a Presumably
what must also be considered here is the strength of the MdE bond being
formed (E ¼ B, Al, Ga), with the greater propensity of boron to undergo

BdH bond cleavage, reflecting the very strong nature (and potential
π-augmentation) of metal–boron bonds.56
Mechanistically, the fundamental processes implicit in EdH bond acti-
vation have also begun to be illuminated, with studies of the interaction of
{HC(MeCDippN)2}GaH2 with cationic rhodium bis(phosphine) frag-
ments, [(R3P)2Rh]+, for example, showing that the degree of GadH bond
activation can be “tuned” by variation in the phosphine ligands, to provide
snapshots of the activation process leading to gallium-to-rhodium transfer of
the two hydrogen atoms.57
REFERENCES
1. For recent reviews relating to BN-containing materials, see, for example: (a) Clark TJ,
Lee K, Manners I. Transition-metal-catalyzed dehydrocoupling: a convenient route to
bonds between main-group elements. Chem Eur J. 2006;12:8634–8648; (b) Marder TB.
Will we soon be fueling our automobiles with ammonia–borane? Angew Chem Int Ed
Engl. 2007;46:8116–8118; (c) Stephens FH, Pons V, Baker RT. Ammonia–borane:
the hydrogen source par excellence? Dalton Trans. 2007;2613–2626; (d) Hamilton
CW, Baker RT, Staubitz A, Manners I. B–N compounds for chemical hydrogen stor-
age. Chem Soc Rev. 2009;38:279–293; (e) Smythe NC, Gordon JC. Ammonia borane as a
hydrogen carrier: dehydrogenation and regeneration. Eur J Inorg Chem. 2010;509–521;
(f ) Staubitz A, Robertson APM, Sloan ME, Manners I. Ammonia-borane and related
compounds as dihydrogen sources. Chem Rev. 2010;110:4023–4078; (g) Staubitz A,
Robertson APM, Manners I. Amine and phosphineborane adducts: new interest
in old molecules. Chem Rev. 2010;110:4079–4124.
2. Aluminium hydride systems: (a) Bogdanović B, Schwickardi MJ. Ti-doped alkali metal
aluminium hydrides as potential novel reversible hydrogen storage materials. J Alloys
Compd. 1997;253:1–9; (b) Lui X, Langmi HW, Beattie SD, Azenwi FF, McGrady
GS, Jensen C. Ti-doped LiAlH4 for hydrogen storage: synthesis, catalyst loading and
cycling performance. J Am Chem Soc. 2011;133:15593–15597. For a study of the tran-
sition metal mediated dehydrogenation of a Ga/N system see, for example: (c) Rudolf D,
Storch G, Kaifer E, Himmel H-J. Synthesis of molecular gallium hydrides by means of
low-temperature catalytic dehydrogenation. Eur J Inorg Chem. 2012;14:2368–2372.
3. Aldridge S, Downs AJ. Hydrides of the main-group metals: new variations on an old
theme. Chem Rev. 2001;101:3305–3365.
4. See, for example, Alcaraz G, Sabo-Etienne S. Coordination and dehydrogenation of
amine-boranes at metal centers. Angew Chem Int Ed Engl. 2010;49:7170–7179.
5. See, for example: (a) Perutz R, Sabo-Etienne S. The σ-CAM mechanism: σ complexes
as the basis of σ-bond metathesis at late-transition-metal centers. Angew Chem Int Ed
Engl. 2007;46:2578–2592; (b) Lin Z. Transition metal σ-borane complexes. Struct Bond-
ing (Berlin). 2008;130:123–148; (c) Alcaraz G, Sabo-Etienne S. NMR: a good tool to
ascertain σ-silane or σ-borane formulations? Coord Chem Rev. 2008;252:2395–2409;
(d) Pandey KK. Transition metal-σ-borane complexes. Coord Chem Rev.
2009;253:37–55; (e) Alcaraz G, Grellier M, Sabo-Etienne S. Bis σ-bond dihydrogen
and borane ruthenium complexes: bonding nature, catalytic applications, and reversible
hydrogen release. Acc Chem Res. 2009;42:1640–1649.
6. (a) Kubas GJ, Ryan RR, Swanson BI, Vergamini PJ, Wasserman HJ. Characterization of
the first examples of isolable molecular hydrogen complexes, M(CO)3(PR3)2(H2)
(M ¼ molybdenum or tungsten; R ¼ Cy or isopropyl). Evidence for a side-on bonded

dihydrogen ligand. J Am Chem Soc. 1984;106:451–452. (b) Kubas GJ. Metal Dihydrogen
and σ-Bond Complexes: Structure, Theory and Reactivity. New York, NY: Kluwer
Academic/Plenum Publishers; 2001.
7. (a) Crabtree RH. The organometallic chemistry of alkanes. Chem Rev.
1985;85:245–269. (b) Crabtree RH. Transition metal complexation of σ-bonds. Angew
Chem Int Ed Engl. 1993;32:789–805. (c) Arndtsen BA, Bergman RG, Mobley TA,
Peterson TH. Selective intermolecular carbon-hydrogen bond activation by synthetic
metal complexes in homogeneous solution. Acc Chem Res. 1995;28:154–162.
(d) Hall C, Perutz RN. Transition metal alkane complexes. Chem Rev.
1996;96:3125–3146. (e) Shilov AE, Shul’pin GB. Activation of C-H bonds by metal
complexes. Chem Rev. 1997;97:2879–2932. (f ) Jones WD. Isotope effects in CH
bond activation reactions by transition metals. Acc Chem Res. 2003;36:140–146.
(g) Labinger JA, Bercaw JE. Understanding and exploiting C-H bond activation.
Nature. 2002;417:507–514. (h) Crabtree RH. Organometallic alkane CH activation.
J Organomet Chem. 2004;689:4083–4091. (i) Cowan AJ, George MW. Formation and
reactivity of organometallic alkane complexes. Coord Chem Rev.
2008;252:2504–2511. (j) See also: Proc Natl Acad Sci USA. 2007;104(17):6899–6973
(coordination of saturated molecules special issue).
8. (a) Schubert U. η2-coordination of Si-H σ bonds to transition metals. Adv Organomet
Chem. 1990;30:151–187. (b) McGrady GS, Guilera G. The multifarious world of tran-
sition metal hydrides. Chem Soc Rev. 2003;32:383–392.
9. Marks TJ, Kolb JR. Covalent transition metal, lanthanide, and actinide tetrahydroborate
complexes. Chem Rev. 1977;77:263–293.
10. (a) Irvine GJ, Lesley MJG, Marder TB, et al. Transition metalboryl compounds: syn-
thesis, reactivity, and structure. Chem Rev. 1998;98:2685–2722. (b) Kays DL, Aldridge S.
Transition metal boryl complexes. Struct Bond (Berlin, Ger). 2008;130:29–122.
(c) Dang L, Lin Z, Marder TB. Boryl ligands and their roles in metal-catalysed borylation
reactions. Chem Commun. 2009;3987–3995. (d) Braunschweig H, Dewhurst RD,
Schneider A. Electron-precise coordination modes of boron-centered ligands. Chem
Rev. 2010;110:3924–3957.
11. See, for example: (a) Beletskaya I, Pelter A. Hydroborations catalysed by transition metal
complexes. Tetrahedron. 1997;53:4957–5026; (b) Mkhalid IAI, Barnard JH, Marder TB,
Murphy JM, Hartwig JF. C–H activation for the construction of C–B bonds. Chem Rev.
2010;110:890–931.
12. Alcaraz G, Helmstedt U, Clot E, Vendier L, Sabo-Etienne S. A terminal borylene ruthe-
nium complex: from B–H activation to reversible hydrogen release. J Am Chem Soc.
2008;130:12878–12879.
13. (a) Tang CY, Thompson AL, Aldridge S. Dehydrogenation of saturated CC and BN
bonds at cationic N-heterocyclic carbene stabilized M(III) centers (M ¼ Rh, Ir). J Am
Chem Soc. 2010;132:10578–10591. (b) O’Neill M, Addy DA, Riddlestone IM,
Kelly M, Phillips N, Aldridge S. Borane to boryl hydride to borylene dihydride: explicit
demonstration of boron-to-metal α-hydride migration in aminoborane activation.
J Am Chem Soc. 2012;133:11500–11503. (c) Addy DA, Bates JI, Kelly MJ,
Riddlestone IM, Aldridge S. Aminoborane σ complexes: significance of hydride
co-ligands in dynamic processes and dehydrogenative borylene formation.
Organometallics. 2013;32:1583–1586.
14. For an initial report of (unsupported) alane coordination at a transition metal centre see:
P€orschke K-R, Kleimann W, Tsay Y-H, Kr€ uger C, Wilke G. Zur Lewis-acidität von
nickel(0). XII. Dimethylaluminiumhydrid-komplexe von nickel(0). Chem Ber.
1990;123:1267–1273.
15. For an initial report of gallane coordination at a transition metal centre see:
Ueno K, Yamaguchi T, Uchiyama K, Ogino H. Synthesis and structure of
(OC)5W(η1-GaH3(quinuclidine)): the first gallane-coordinated transition-metal

complex. Organometallics. 2002;21:2347–2349; See also: (b) Muraoka T, Ueno
K. Gallane-coordinated transition metal complexes and related compounds. Coord
Chem Rev. 2010;254:1348–1355.
16. For Al-H activation at a main group metal centre see: (a) Chu T, Korobkov I,
Nikonov GI. Oxidative addition of σ bonds to an Al(I) center. J Am Chem Soc.
2014;136:9195–9202; and (b) Xiong Y, Yao S, Driess M. Versatile conversion of
N-heterocyclic silylene to silyl metal compounds by insertion of divalent silicon into
metal-carbon and metal-hydrogen bonds. Chem Eur J. 2012;18:3316–3320. Reductive
elimination of RH in the formation of Al(I) species has been reported by Fischer and
Frenking: (c) Ganesamoorthy C, Loerke S, Gemel C, Jerabek P, Winter M,
Frenking G, Fischer RA. Reductive elimination: a pathway to low-valent aluminium
species. Chem Commun. 2013;49:2858–2860.
17. Aldridge S, Downs AJ. The Group 13 Metals Aluminium, Gallium, Indium and Thallium:
Chemical Patterns and Peculiarities. Chichester, UK: Wiley; 2011.
18. Turner J, Abdalla JAB, Bates JI, et al. Formation of sub-valent carbenoid ligands by
metal-mediated dehydrogenation chemistry: coordination and activation of H2Ga
{(NDippCMe)2CH}. Chem Sci. 2013;4:4245–4250.
19. For a collection of recent reviews, see Acc Chem Res. 2012;45(6):777–958, C–H func-
tionalization, notably: (a) Gaillard S, Cazin CSJ, Nolan SP. N-Heterocyclic carbene
gold(I) and copper(I) complexes in C–H bond activation. Acc Chem Res.
2012;45:778–787; (b) Colby DA, Tsai AS, Bergman RG, Ellman JA. Rhodium cata-
lyzed chelation-assisted C–H bond functionalization reactions. Acc Chem Res.
2012;45:814–825; (c) Hartwig JF. Borylation and silylation of C–H bonds: a platform
for diverse C–H bond functionalizations. Acc Chem Res. 2012;45:864–873;
(d) Hashiguchi BB, Bischof SM, Konnick MM, Periana RA. Designing catalysts for
functionalization of unactivated C–H bonds based on the CH activation reaction. Acc
Chem Res. 2012;45:885–898; (e) Boisvert L, Goldberg KI. Reactions of late transition
metal complexes with molecular oxygen. Acc Chem Res. 2012;45:899–910; (f ) Roizen
JL, Harvey ME, Du Bois J. Metal-catalyzed nitrogen-atom transfer methods for the oxi-
dation of aliphatic C–H bonds. Acc Chem Res. 2012;45:911–922; (g) Neufeldt SR,
Sanford MS. Controlling site selectivity in palladium-catalyzed C–H bond func-
tionalization. Acc Chem Res. 2012;45:936–946; (h) Haibach MC, Kundu S, Brookhart
M, Goldman AS. Alkane metathesis by tandem alkane-dehydrogenation–
olefin-metathesis catalysis and related chemistry. Acc Chem Res. 2012;45:947–958.
See also Chem Rev. 2010;110(2):575–1211, Selective functionalization of C–H bonds.
20. (a) Bernskoetter WH, Schauer CK, Goldberg KI, Brookhart M. Characterization of
a rhodium(I) σ-methane complex in solution. Science. 2009;326:553–556. For an
example of a crystallographically characterized alkane complex see: (b) Pike SD,
Thompson AL, Algarra AG, Apperley DC, Macgregor SA, Weller AS. Synthesis
and characterization of a rhodium(I) σ-alkane complex in the solid state. Science.
2012;337:1648–1651.
21. Shimoi M, Nagai S, Ichikawa M, et al. Coordination compounds of mono-
boraneLewis base adducts: syntheses and structures of [M(CO)5(η1-BH3L)]
(M ¼ Cr, Mo, W; L ¼ NMe3, PMe3, PPh3). J Am Chem Soc. 1999;121:11704–11712.
22. He XM, Hartwig JF. True metal-catalyzed hydroboration with titanium. J Am Chem Soc.
1996;118:1696–1702.
23. Hartwig JF, Muhoro GN, He XM, Eisenstein O, Bosque R, Maseras F. Catecholborane
bound to titanocene. Unusual coordination of ligand σ-bonds. J Am Chem Soc.
1996;118:10936–10937.
24. Bissinger P, Braunschweig H, Kupfer T, Radacki K. Monoborane NHC adducts in the
coordination sphere of transition metals. Organometallics. 2010;29:3987–3990.
25. Kakizawa T, Kawano Y, Shimoi M. Syntheses and structures of manganese complexes of

boraneLewis base adducts, [CpMn(CO)2(η1-BH3L)] (L ¼ NMe3, PMe3).
26. (a) Schubert U, Ackermann K, Woerle B. A long silicon-hydrogen bond or a short
silicon-hydrogen nonbond? Neutron-diffraction study of (η5CH3C5H4)(CO)2(H)-
MnSiF(C6H5)2. J Am Chem Soc. 1982;104:7378–7380. (b) Scherer W, Eickerling G,
Tafipolsky M, McGrady GS, Sirsch P, Chatterton NP. Elucidation of the bonding in
Mn(η2-SiH) complexes by charge density analysis and T1 NMR measurements: asym-
metric oxidative addition and anomeric effects at silicon. Chem Commun.
2006;2986–2988.
27. Schilling BER, Hoffmann R, Lichtenberger DL. CpM(CO)2(ligand)
(Cp ¼ cyclopentadienyl, M ¼ metal) complexes. J Am Chem Soc. 1979;101:585–591.
28. Kawano Y, Hashiva M, Shimoi M. Syntheses and reactivity of cationic bor-
aneruthenium complexes [(η5-C5R5)Ru(PMe3)2(η1-BH3EMe3)][BArf4] (R ¼ H,
Me; E ¼ N, P; BArf4 ¼ [B{3,5-C6H3(CF3)2}4]). Organometallics. 2006;25:4420–4426.
29. See for example: (a) Staubitz A, Sloan ME, Robertson APM, et al. Catalytic
dehydrocoupling/dehydrogenation of N-methylamine-borane and ammonia-borane:
synthesis and characterization of high molecular weight polyaminoboranes. J Am Chem
Soc. 2010;132:13332–13345; (b) Staubitz A, Soto AP, Manners I. Iridium-catalyzed
dehydrocoupling of primary amine–borane adducts: a route to high molecular weight
polyaminoboranes, boron–nitrogen analogues of polyolefins. Angew Chem Int Ed Engl.
2008;47:6212–6215; (c) Sewell LJ, Lloyd-Jones GC, Weller AS. Development of a
generic mechanism for the dehydrocoupling of amine-boranes: a stoichiometric, cata-
lytic, and kinetic study of H3BNMe2H using the [Rh(PCy3)2]+ fragment. J Am Chem
Soc. 2012;134:3598–3610; (d) Huertos MA, Weller AS. Intermediates in the
Rh-catalysed dehydrocoupling of phosphine–borane. Chem Commun.
2012;48:7185–7187; (e) Sewell LJ, Huertos MA, Dickinson ME, Weller AS, Lloyd-
Jones GC. Dehydrocoupling of dimethylamine borane catalyzed by Rh(PCy3)2H2Cl.
Inorg Chem. 2013;52:4509–4516; (f ) Hooper TN, Huertos MA, Jurca T, Pike SD,
Weller AS, Manners I. Effect of the phosphine steric and electronic profile on
the Rh-promoted dehydrocoupling of phosphine–boranes. Inorg Chem.
2014;53:3716–3729; (g) Johnson HC, Leitao EM, Whittell GR, Manners I, Lloyd-Jones
GC, Weller AS. Mechanistic studies of the dehydrocoupling and dehydropolymerization
of amine–boranes using a [Rh(Xantphos)]+ catalyst. J Am Chem Soc.
2014;136:9078–9093.
30. (a) Douglas TM, Chaplin AB, Weller AS. Amine-borane σ-complexes of rhodium. Rel-
evance to the catalytic dehydrogenation of amine-boranes. J Am Chem Soc.
2008;130:14432–14433. (b) Douglas TM, Chaplin AB, Weller AS, Yang X,
Hall MB. Monomeric and oligomeric amine–borane σ-complexes of rhodium. Interme-
diates in the catalytic dehydrogenation of amine–boranes. J Am Chem Soc.
2009;131:15440–15456. (c) Tang CY, Thompson AL, Aldridge S. Rhodium and
iridium aminoborane complexes: coordination chemistry of BN alkene analogues.
Angew Chem Int Ed Engl. 2010;49:921–925. (d) Chaplin AB, Weller AS. Amine- and
dimeric amino-borane complexes of the {Rh(PiPr3)2}+ fragment and their
relevance to the transition-metal-mediated dehydrocoupling of amine-boranes. Inorg
Chem. 2010;49:1111–1121. (e) Johnson HC, Robertson APM, Chaplin AB, et al.
Catching the first oligomerization event in the catalytic formation of polyaminoboranes:
H3BNMeHBH2NMeH2 bound to iridium. J Am Chem Soc. 2011;133:11076–11079.
(f ) Dallanegra R, Robertson APM, Chaplin AB, Manners I, Weller AS. Tuning the
[L2Rh. . .H3BNR3]+ interaction using phosphine bite angle. Demonstration by the cat-
alytic formation of polyaminoboranes. Chem Commun. 2011;47:3763–3765.
(g) Tang CY, Phillips N, Kelly MJ, Aldridge S. Hydrogen shuttling: synthesis and
reactivity of a 14-electron iridium complex featuring a bis(alkyl) tethered ligand. Chem

Commun. 2012;48:11999–12001. (h) Johnson HC, McMullin CL, Pike SD,
Macgregor SA, Weller AS. Dehydrogenative boron homocoupling of an amine-borane.
Angew Chem Int Ed Engl. 2013;52:9776–9780. (i) Algarra AG, Sewell LJ, Johnson HC,
Macgregor SA, Weller AS. A combined experimental and computational study of flux-
ional processes in sigma amine–borane complexes of rhodium and iridium. Dalton Trans.
2014;43:11118–11128. (j) Phillips N, Tang CY, Tirfoin R, et al. Modulating reactivity
in iridium bis(N-heterocyclic carbene) complexes: influence of ring size on E-H bond
activation chemistry. Dalton Trans. 2014;43:12288–12298.
31. Muhoro CN, Hartwig JF. Synthesis, structure, and reactivity of [Cp2Ti(HBcat)(PMe3)]:
a monoborane σ complex. Angew Chem Int Ed Engl. 1997;36:1510–1512.
32. Schlecht S, Hartwig JF. σ-Borane complexes of manganese and rhenium. J Am Chem Soc.
2000;122:9435–9443.
33. McGrady GS, Sirsch P, Chatterton NP, et al. Nature of the bonding in metal-silane
σ-complexes. Inorg Chem. 2009;48:1588–1598.
34. (a) Alcaraz G, Clot E, Helmstedt U, Vendier L, Sabo-Etienne S. Mesitylborane as a
Bis(σ-BH) ligand: an unprecedented bonding mode to a metal center. J Am Chem
Soc. 2007;129:8704–8705. See also: (b) Gloaguen Y, Benac-Lestrille G, Vendier L,
et al. Monosubstituted borane ruthenium complexes RuH2(η2:η2-H2BR)(PR0 3)2: a
general approach to the geminal bis(σ-B–H) coordination mode. Organometallics.
2013;32:4868–4877; (c) Buil ML, Cardo JJF, Esteruelas MA, Fernandez I, Onate E.
Hydroboration and hydrogenation of an osmium–carbon triple bond: osmium chemistry
of a bis-σ-borane. Organometallics. 2015;34:547–550.
35. (a) Hesp KD, Rankin MA, McDonald R, Stradiotto M. Synthesis and characterization of
a cationic ruthenium complex featuring an unusual bis(η2-BH) monoborane ligand. Inorg
Chem. 2008;47:7471–7473. (b) Hesp KD, Kannemann FO, Rankin MA, McDonald R,
Ferguson MJ, Stradiotto M. Probing mesitylborane and mesitylborate ligation within the
coordination sphere of Cp*Ru(PiPr3)+: a combined synthetic, X-ray crystallographic,
and computational study. Inorg Chem. 2011;50:2431–2444.
36. (a) Alcaraz G, Vendier L, Clot E, Sabo-Etienne S. Ruthenium bis(σ-B-H) aminoborane
complexes from dehydrogenation of amine–boranes: trapping of H2B-NH2. Angew
Chem Int Ed Engl. 2010;49:918–920. (b) Esteruelas MA, Fernandez-Alvarez FJ,
Lopez AM, Mora M, Onate E. Borinium cations as σ-BH ligands in osmium com-
plexes. J Am Chem Soc. 2010;132:5600–5601. (c) Alcaraz G, Chaplin AB, Stevens CJ,
et al. Ruthenium, rhodium, and iridium bis(σ-BH) diisopropylaminoborane com-
plexes. Organometallics. 2010;29:5591–5595. (d) Stevens CJ, Dallanegra R,
Chaplin AB, et al. [Ir(PCy3)2(H)2(H2B-NMe2)]+ as a latent source of aminoborane:
probing the role of metal in the dehydrocoupling of H3BNMe2H and retrodimerisation
of [H2BNMe2]2. Chem Eur J. 2011;17:3011–3020. (e) Bénac-Lestrille G, Helmstedt U,
Vendier L, Alcaraz G, Clot E, Sabo-Etienne S. Probing mesitylborane and mesitylborate
ligation within the coordination sphere of Cp*Ru(PiPr3)+: a combined synthetic, X-ray
crystallographic, and computational study. Inorg Chem. 2011;50:11039–11045.
(f ) Tang CY, Phillips N, Bates JI, Thompson AL, Gutmann MJ, Aldridge S.
Dimethylamine borane dehydrogenation chemistry: syntheses, X-ray and neutron dif-
fraction studies of 18-electron aminoborane and 14-electron aminoboryl complexes.
Chem Commun. 2012;48:8096–8098. (g) Addy DA, Bates JI, Kelly MJ, et al. Synthesis
and reactivity of half-sandwich ruthenium κ2-aminoborane complexes. Aus J Chem.
2013;66:1211–1218. (h) Joost M, Alcaraz C, Vendier L, Poblador-Bahamonde A,
Clot E, Sabo-Etienne S. Synthesis of a ruthenium bis(diisopropylamino(isocyano)
borane) complex from the activation of an amino(cyano)borane. Dalton Trans.
2013;42:776–781. (i) Esteruelas MA, Fernandez I, Lopez AM, Malka M, Onate E.
Osmium-promoted dehydrogenation of amine–boranes and B–H bond activation of
the resulting amino–boranes. Organometallics. 2014;33:1104–1107. (j) Cassen A,

Vendier L, Daran J-C, et al. B–C bond cleavage and Ru–C bond formation from a phos-
phinoborane: synthesis of a bis-σ borane aryl-ruthenium complex. Organometallics.
2014;33:7157–7163.
37. For an early report examining aminoborane interactions with transition metals see:
Schmid G. Metall-bor-verbindungen, VIII. Aminoborane als π-liganden in metal-
lkomplexen. Chem Ber. 1970;103:528–534.
38. Westwood NPC, Westiuk NH. Aminoborane: helium (He I) photoelectron spectrum
and semiempirical/ab initio investigation of the ground and first excited cationic states.
J Am Chem Soc. 1986;108:891–894.
39. Vidovic D, Addy DA, Krämer T, McGrady J, Aldridge S. Probing the intrinsic structure
and dynamics of aminoborane coordination at late transition metal centers: mono(σ-BH)
binding in [CpRu(PR3)2(H2BNCy2)]+. J Am Chem Soc. 2011;133:8494–8497.
40. (a) Knorr JR, Merola JS. Synthesis and structure of a [(1,2-phenylenedioxy)boryl]
iridium hydride complex: a model system for studying catalytic hydroboration.
Organometallics. 1990;9:3008–3010. (b) Baker RT, Ovenall DW, Calabrese JC, et al.
Boryliridium and boraethyliridium complexes fac-[IrH2(PMe3)3(BRR0 )] and fac-[IrH
(PMe3)3(η2-CH2BHRR0 )]. J Am Chem Soc. 1990;112:9399–9400.
41. For other neutron diffraction studies of coordinated B–H bonds, see: (a) Lam WH,
Shimada S, Batsanov AS, et al. Accurate molecular structures of 16-electron rhodium
hydrido boryl complexes: low-temperature single-crystal X-ray and neutron diffraction
and computational studies of [(PR3)2RhHCl(Boryl)] (Boryl ¼ Bpin, Bcat). Organometallics.
2003;22:4557–4568; (b) Hebden TJ, Denney TJ, Pons V, et al. σ-Borane complexes
of iridium: synthesis and structural characterization. J Am Chem Soc.
2008;130:10812–10820.
42. Hartwig JF, Cook KS, Hapke M, et al. Rhodium boryl complexes in the catalytic. Ter-
minal functionalization of alkanes. J Am Chem Soc. 2005;127:2538–2552.
43. Braunschweig H, Forster M, Kupfer T, Seeler F. Borylene transfer under thermal con-
ditions for the synthesis of rhodium and iridium borylene complexes. Angew Chem Int Ed
Engl. 2008;47:5981–5983.
44. See, for example: (a) Belsky VK, Erofeev AB, Bulychev BM, Soloveichik GL. Synthesis
and molecular structure of solvated hydride complexes of aluminium and di-η5-
cyclopentadienylyttrium. J Organomet Chem. 1984;265:123–133; (b) Belskii VK,
Bulychev BM, Erofeev AB, Soloveichik GL. Alumohydride complex of yttrium with
three-coordinated hydrogen atoms. The crystal and molecular structure of {[(η5-
C5H5)2Y(μ3-H)][μ2-H)AlH2OC4H8]}2. J Organomet Chem. 1984;268:107–111;
(c) Khan K, Raston CL, McGrady JE, Skelton BW, White AH. Hydride-bridged
heterobimetallic complexes of zirconium and aluminum. Organometallics.
1997;16:3252–3254; (d) Plois M, Wiegand T, Wolf R. Novel ruthenium(II) aluminate
anions: building blocks of unique cage structures. Organometallics. 2012;31:8469–8477.
45. (a) Lobkovskii B, Soloveichik GL, Erofeev AB, Bulychev BM, Bel’ski VK. The crystal and
molecular structure of the complex of yttrium biscyclopentadienyl chloride with alumin-
ium hydride monoetherate [((η5-C5H5))2YCl]2AlH3—OEt2. J Organomet Chem.
1982;235:151–159. (b) Lobkovskii EB, Soloveichik GL, Sisov AI, Bulychev BM,
Gusev AI, Kirillova NI. Structural chemistry of bimetallic hydride complexes of
titanium and aluminium: I. Crystal and molecular structure of [(η5-C5H5)2,
Ti(μ-H)2AlH2]2 (CH3)2NCH2CH2N(CH3)2C6H6. J Organomet Chem. 1984;265:167–173.
46. (a) Burlakov VV, Kaleta K, Beweries T, et al. Reactions of five-membered meta-
llacyclocumulenes Cp2M(η4-t-Bu-C4-t-Bu) (M ¼ Ti, Zr) with diisobutylaluminum
hydride. Organometallics. 2011;30:1157–1161. (b) Arndt P, Spannenberg A,
Baumann W, et al. Reactions of zirconocene 2-vinylpyridine complexes with
diisobutylaluminum hydride and fluoride. Organometallics. 2004;23:4792–4795.
47. Yow S, Gates SJ, White AJP, Crimmin MR. Zirconocene dichloride catalyzed
hydrodefluorination of Csp2-F bonds. Angew Chem Int Ed Engl. 2012;51:12559–12563.
48. (a) Steinke T, Gemel C, Cokoja M, Winter M, Fischer RA. AlCp* as a directing ligand:
C-H and Si-H bond activation at the reactive intermediate [Ni(AlCp*)3]. Angew Chem
Int Ed Engl. 2004;43:2299–2302. (b) Steinke T, Cokoja M, Gemel C, et al. C-H acti-
vated isomers of [M(AlCp*)5] (M ¼ Fe, Ru). Angew Chem Int Ed Engl.
2005;44:2943–2946.
49. (a) Riddlestone IM, Edmonds S, Kaufman PA, et al. σ-Alane complexes of chromium,
tungsten, and manganese. J Am Chem Soc. 2012;134:2551–2554. (b) Abdalla JAB,
Riddlestone IM, Tirfoin R, Phillips N, Bates JI, Aldridge S. Al-H σ-bond coordination:
expanded ring carbene adducts of AlH3 as neutral bi- and tri-functional donor
ligands. Chem Commun. 2013;49:5547–5549. (c) Riddlestone IM, Urbano J,
Phillips N, et al. Salt metathesis for the synthesis of M–Al and M–H–Al bonds. Dalton
Trans. 2013;42:249–258. (d) Abdalla JAB, Riddlestone IM, Turner J, et al. Coordi-
nation and activation of Al-H and Ga-H bonds. Chem Eur J. 2014;20:17624–17634.
50. (a) Cordero B, Gómez V, Platero-Prats AE, et al. Covalent radii revisited. Dalton Trans.
2008;2832–2838. (b) Emsley J. The Elements. 3rd ed. Oxford: OUP; 1998.
51. (a) Nako AE, Gates SJ, White AJP, Crimmin MR. Preparation and properties of a series
of structurally diverse aluminium hydrides supported by β-diketiminate and bis(amide)
ligands. Dalton Trans. 2013;42:15199–15206. (b) Nako AE, Tan QW, White AJP,
Crimmin MR. Weakly coordinated zinc and aluminum σ-complexes of copper(I).
52. Cui C, Roesky HW, Schmidt H-G, Noltemeyer M, Hao H, Cimpoesu F. Synthesis and
structure of a monomeric aluminum(I) compound [{HC(CMeNAr)2}Al] (Ar ¼ 2,6-
iPr2C6H3): a stable aluminum analogue of a carbene. Angew Chem Int Ed Engl.
2000;39:4274–4276.
53. (a) Ruff JK, Hawthorne MF. The amine complexes of aluminum hydride. I. J Am Chem
Soc. 1960;82:2141–2144. (b) Greenwood NN, Storr A, Wallbridge MGH.
Trimethylamine adducts of gallane and trideuteriogallane. Inorg Chem.
1963;2:1036–1039. (c) Shriver DF, Parry RW. Preparation and characterization of
trimethylamine gallane and bistrimethylamine gallane’. Inorg Chem. 1963;2:1039–1042.
54. (a) Pulham CR, Downs AJ, Goode MJ, Rankin DWH, Robertson HE. Gallane: syn-
thesis, physical and chemical properties, and structure of the gaseous molecule Ga2H6 as
determined by electron diffraction. J Am Chem Soc. 1991;113:5149–5162. (b) Downs AJ,
Pulham CR. The hydrides of aluminium, gallium, indium, and thallium: a re-evaluation.
Chem Soc Rev. 1994;23:175–184.
55. Atwood JL, Bott SG, Elms FM, Jones C, Raston CL. Tertiary amine adducts of gallane:
gallane-rich [{GaH3}2(TMEDA)] (TMEDA ¼ N,N,N0 ,N0 -tetramethylethylenediamine)
and thermally robust [GaH3(quinuclidine)]. Inorg Chem. 1991;30:3792–3793.
56. Rablen PR, Hartwig JF, Nolan SP. First transition metal-boryl bond energy and
quantitation of large differences in sequential bond dissociation energies of boranes.
J Am Chem Soc. 1994;116:4121–4122.
57. Abdalla JAB, Edwards AJ, Aldridge S. Unpublished results.
CHAPTER TWO
Singular Metal Activation

of Diboron Compounds
Stephen A. Westcotta, Elena Fernándezb,*
a
Department of Chemistry and Biochemistry, Mount Allison University, Sackville,
New Brunswick, Canada
b
Departament Quı́mica Fı́sica i Inorgànica, University Rovira i Virgili, Tarragona, Spain
*Corresponding author: e-mail address: [email protected]
Contents
1. Introduction: The Activation of Cl2B–BCl2 and Beyond 39
2. General Trends on Activation of Symmetrical Diboron Compounds 42
2.1 Metal Activation of Tetra(alkoxy)diborons 43
2.2 Metal Activation of Halide- or Amine-Substituted Diboron Compounds 70
2.3 Nanoparticle Activation 73
3. Precise Activation of Unsymmetrical Dialkoxy-diamino-diboron Compounds 77
4. Summary and Outlook 79
Acknowledgments 80
References 80
1. INTRODUCTION: THE ACTIVATION OF Cl2B–BCl2

AND BEYOND
Compounds containing direct boron–boron bonds have been of con-
siderable interest for many years owing to their unusual electron-deficient
nature. A successful proof of concept was the eminent reactivity between
Cl2B–BCl2 and ethylene representing the first addition of a borane reagent
to an alkene,1 even before any hydroboration reaction between B2H6 and
olefins was described.2 Despite the fact that the diborated compound formed
at 80 °C was characterized as Cl2B(CH2)(CH2)BCl2, the authors deferred
to assign a name to the new organoboron compound until “a committee,
considering nomenclature of boron compounds in 1954, had reached a final
decision.” Looking at this incipient novel reactivity, the addition of Cl2B–
BCl2 was carried out to a wider range of alkenes, including diboration of
cyclopropene and double addition to butadiene.3 For ethyne, cis-addition
Advances in Organometallic Chemistry, Volume 63 # 2015 Elsevier Inc. 39

ISSN 0065-3055 All rights reserved.
http://dx.doi.org/10.1016/bs.adomc.2015.02.001
40 Stephen A. Westcott and Elena Fernández
of B2Cl4 was defined and later extended to other terminal alkynes.4 A first
hypothesis for the activation of the diboron tetrachloride was suggested by
Feeney, Holliday, and Marsden in 1961, indicating that the initial fission of
BdB bond and then addition to olefins were unlikely.5 Based on the
observed rapid reaction of Cl2B–BCl2 with ethylene at low temperature,
these authors postulated as a first stage the π-donation from the olefin into
the vacant p-type orbital of the boron atoms, since these being on adjacent
bonded atoms might constitute a “vacant π-orbital.” As a consequence, this
interaction would give a π-complex (1) which might either dissociate again
or suffer fission of the B–B to give the product 2 (Scheme 1).
In parallel, Fox and Wartik evidenced a slow interaction between Cl2B–
BCl2 and aromatic compounds, leading to a single electrophilic substitution
product C6H5BCl2 from benzene, but to a double addition product from
naphthalene toward complete saturation of one ring.6 Subsequently, Zeldin
and Wartik assumed cis-addition of Cl2B–BCl2 to the π-bonds of the con-
jugated systems in 1,3-cyclohexadiene and naphthalene.7 Again, the rapidity
of the reaction between the diboron tetrachloride and the carbon–carbon
π-bond of the conjugated system, even at very low temperatures, weighed
in the author’s criteria against B–B rupture prior to addition. Besides this
intuitively favored activation of the diboron tetrachloride, Rudolph simul-
taneously proposed a four-center transition state 3 (Fig. 1).8 The favored ori-
entation in the suggested transition state (Fig. 1) would seem to require that
Cl2B–BCl2 assumes a near-planar configuration,9 the driving force for
which should be the maximum orbital overlap between the vacant
p-orbitals on the boron atoms and the basic site of the π-orbital on the
hydrocarbon, represented in structure 4 (Fig. 1).10
In contrast to the above mechanism, which must give rise to a cis product,
a process involving prior homolytic cleavage of the boron–boron bond to
generate free dichloroboryl radicals would, because of the opportunity
for free rotation about the carbon–carbon single bond, not be expected
π-complex
Cl Cl Cl Cl
Cl2B BCl2
B B B B
Cl Cl Cl Cl R2C CR⬘2
+
R2C CR⬘2 R2C CR⬘2 2
1
Scheme 1 Postulated activation of Cl2B–BCl2 with olefins toward diboration reaction.
Singular Metal Activation of Diboron Compounds 41
Four-center
transition state
Cl Cl
B B
C C
Cl Cl
H H
C C
R B B
R
3 4
Figure 1 Suggested concerted interaction of Cl2B–BCl2 with olefins.
Cl Cl R2C CR⬘2
Cl
B B −
+ B B
Cl Cl Cl2 Cl
+
R2C CR⬘2
5
Scheme 2 Unlikely heterolytic cleavage of Cl2B–BCl2.
to proceed in a stereospecific manner. Furthermore, calculation carried

out on bond energy does not favor dissociation as an initiating step
(ΔΗB–B ¼ 79.0 kcal/mol).11 The activation of Cl2B–BCl2 involving the for-
mation of a cyclic organoboronium ion 5 (Scheme 2) was also discarded
because of the lack of trans-diborated compounds observed.
The activation of Cl2B–BCl2 with ferrocene has also been suggested to
proceed through a π-complex, 6 to form the ferrocenyldichloroborane 7,
discarding other intermediates of lower stability where Fe directly interacts
with B (Scheme 3).12
The slower reactivity observed for the addition of Cl2B–BCl2 to the
haloolefins might be a consequence of the less favored formation of the
π-complex in this case. The diborated product suffers an elimination of
trihaloborane, and subsequent addition of Cl2B–BCl2 to the resulting
vinyltrihaloborane gives as a final product the poly(dihaloboryl)ethane.13
The π-acidity of Cl2B–BCl2 and the fact that it was the first isolated com-
pound containing a localized two-center-two-electron (2c/2e) BdB bond
gave rise to tremendous interest into routes to prepare organoboron com-
pounds from this tetra(chloro)diboron.14–17 This issue was further revisited
by Morrison highlighting the possibility to use Cl2B–BCl2 as the precursor
for the synthesis of Br2B–BBr2, F2B–BF2, (R2N)2B–B(NR2)2, and
(RO)2B–B(OR)2 when reacted with BBr3, SbF3, dialkylamines, and
Cl Cl
B B
Cl Cl
+ Cl Cl
B B
Cl Cl Cl Cl BCl2
B
Fe Fe Fe Fe + HBCl2
B
Cl Cl
6 7
Scheme 3 Activation of Cl2B–BCl2 with ferrocene.
alcohols, respectively.18 However, at that stage, progress became limited by

the instability and restricted availability of Cl2B–BCl2, which was originally
produced by an electric discharge through BCl3 at low temperatures,19–21
and a further improved method from copper vapor and BCl3.22,23
A more accessible diboron compound was then required to continue with
the expected applicability on organoborane synthesis although the activation
model should be conceptually changed.
2. GENERAL TRENDS ON ACTIVATION OF SYMMETRICAL

DIBORON COMPOUNDS
The stability of diboron compounds X2B–BX2 depends on the nature
of the substituent on B, decreasing from X ¼ R2N, RO > F > aryl, alkyl, Cl,
whereupon Cl2B–BCl2 being the most prone toward disproportionation.
Organodiboron compounds, R2B–BR2, are stable only when sterically
demanding R groups, such as t-Bu, CH2-t-Bu, and mesityl, are protecting
the B atom.24–26 On the contrary, tetra(amino)diborons21,27,28 and
tetra(alkoxy)diborons21,29–32 show a remarkable stability due to the exten-
sive π-type overlap with the neighboring nitrogen or oxygen atoms which
stabilize the boron atom. The concomitant consequences are lower reactiv-
ity against unsaturated substrates, but the resulting organoboron compounds
become generally air and water stable and amenable to chromatography.
The new scenario for tetra(amino)diboron and tetra(alkoxy)diboron com-
pounds shows a less π-acidic B–B system that might justify the unlikely for-
mation of the π-complex between (R2N)2B–B(NR2)2 or (RO)2B–B(OR)2
and the olefins, diminishing the direct reactivity toward diboration. The
BdB bond in tetrakis(dimethylamino)diboron is so stable that this diboron
compound is generally used to prepare other boron–boron linkages.30,33
O O
B B
O O
B2pin2 9
O O
B B Stability Reactivity
O O
B2cat2 8
Cl Cl
B B
Cl Cl
Cl2B−BCl2
Figure 2 Relative Lewis acidity of Cl2B–BCl2 and tetra(alkoxy)diboron compounds

B2cat2 and B2pin2.
However, tetra(alkoxy)diboron compounds, such as B2cat234 (cat ¼ 1,2-

O2C6H4) (8) and B2pin235 (pin ¼ 1,2-O2C2Me4) (9) (Fig. 2), have emerged
as the synthetic reagents of choice to react with unsaturated substrates,
because of the appropriate balance between stability and reactivity parame-
ters. In particular, the pinacolato derivative 9, despite the fact that is slightly
less Lewis acidic than 8 and therefore less reactive, provides the widest range
of organoboron compound synthesis because of their great stability
(Scheme 4).36,37
2.1 Metal Activation of Tetra(alkoxy)diborons

Taking into consideration that boron–boron dissociation energy in
tetra(alkoxy)diboron compounds has been estimated to be slightly higher
than that of the corresponding data for other diboron compounds,38,39
together with the low Lewis acidity of the boron centers, a new model
to activate the (RO)2B–B(OR)2 has to be considered. In fact, an external
activator of the tetra(alkoxy)diboron is required to accomplish its addition
to unsaturated substrates. The activators can be considered transition metals
or Lewis bases (LBs), and the mode of interaction can be displayed as a
homolytic or as a heterolytic B–B cleavage, as it is illustrated for B2pin2
in Scheme 5. When a transition metal complex, characterized by a low-
valent metal, interacts with the nonpolar tetra(alkoxy)diboron species, a
Bpin + XBpin
CO + O(Bpin)2
X
CO2
R R
Bpin Bpin R R
R H
B2pin2
Bpin Bpin
R H R
R
R
O R
Bpin R
R Bpin R Bpin O R
Bpin Bpin
Bpin
Scheme 4 Selected synthetic applications of B2pin2.
A B n+
C
n+ M X
M LB
O O O O O O
B B B B B B
O O O O O O
n+
(n−2)+ M
M X LB
− O
B + B B + B
B B O
O O O O O O O O
O O
Scheme 5 Activation modes for B2pin2. (A) Activation by oxidative addition,

(B) activation by σ-bond metathesis, and (C) activation by Lewis bases.
three-centered σ-complex is invoked followed by intramolecular B–B

cleavage to form the corresponding oxidized metal complex
(Scheme 5A). As a product of this oxidative addition, the resulting two boryl
ligands will be mutually cis, although subsequent isomerization may occur.
Alternatively, a transition metal species that includes a MdX bond
(X ¼ preferentially OR group) can perform a σ-bond metathesis with the
tetra(alkoxy)diboron compound, promoting a heterolytic cleavage of the

B–B with the concomitant formation of a M-boryl species and the resulting
X–B(OR)2 (Scheme 5B). The formation of the tris(alkoxy)borane com-
pound can be considered as the driving force in a sequence where the metal
does not involve any change in its oxidative state. Finally, the addition of an
appropriate LB establishes a selective interaction with one of the B(OR)2
unit from the tetra(alkoxy)diboron, delivering a new Lewis acid–base
adduct, MeO ! Bpin–Bpin, that is characterized by a quaternized
B(sp3) moiety and an enhanced nucleophilic B(sp2) unit (Scheme 5C).
Within the sections 2 and 3, several examples are disclosed to illustrate
the ability of transition metal complexes to transform the unreactive
(RO)2B–B(OR)2 compounds into very reactive species toward the addition
to unsaturated substrates.
2.1.1 Activation by Metal Complexes of Group 10

Miyaura and Suzuki published in 1993 their groundbreaking work40 on the
diboration of alkynes with B2pin2, using a platinum(0) complex [Pt(PPh3)4]
as the activator of the diboron. They were the first to propose a mechanism
involving oxidative addition of the pinBdBpin bond to Pt as the initial step
(Scheme 6) followed by coordination of the alkyne to the bis(boryl)-Pt com-
plex cis-[Pt(Bpin)2(PPh3)2] (10a) (Scheme 6), provoking an insertion of the
unsaturated substrate into the PtdB bond and generating eventually the
cis-1,2-diborated alkene by reductive elimination. The authors demon-
strated the activation of B2pin2 by NMR analysis of the reaction mixture
B2pin2
R R⬘ Pt(0)
Bpin Bpin
Bpin
R R⬘
Pt Bpin
Bpin Pt Bpin
Bpin
Pt Bpin R R⬘
R R⬘
Scheme 6 Proposed mechanism for the Pt(0)-diboration of alkynes with B2pin2.
of Pt(PPh3)4 with 10 equiv. of B2pin2 in toluene at room temperature for

12 h or at 100 °C for 1 h. The 11B NMR spectra exhibited a new signal
at 21.5 ppm besides that for the starting B2pin2 (29.9 ppm).
The same authors exhibited a comparative study on the activation of
(MeO)2B–B(OMe)2 and (Me2N)2B–B(NMe2)2 with the platinum(0) com-
plex [Pt(PPh3)4], and further application to the diboration of 1-octyne. The
results clearly demonstrated that both the tetra(alkoxy)diboron performed in
a similar way (quantitative conversion on the cis-1,2-diborated product,
under 80 °C), but the tetrakis(dimethylamino)diboron was only added
in 7% to the 1-octyne, even at 120 °C.41 The oxidative addition of
(Me2N)2B–B(NMe2)2 to Pt(0) was less efficient, as it was expected, due
to the enhanced stability of the diboron by the π-donation of the amino
groups to the B atoms.
To complement the activation study of tetra(alkoxy)diboron with Pt(0)
complexes, Smith and Iverson disclosed their findings on the reactivity of
B2cat2 with [Pt(η2-CH2]CH2)(PPh3)2], which resulted in the loss of eth-
ylene, even at 80 °C, followed by oxidative addition of the BdB bond to
give the bis(boryl) complex cis-[Pt(Bcat)2(PPh3)2] (10b) (Scheme 7).42,43
The 11B NMR data for 10b provided a broad signal at δ 47.2 ppm, and reac-
tivity studies confirmed that the stoichiometric addition of alkynes led to the
corresponding diborated products. Interestingly, mechanistic studies favored
a mechanism where phosphine dissociation generated a three-coordinate
intermediate that mediated the alkyne insertion.
The molecular structure of similar bis(boryl) complexes cis-[Pt(B-4-
Butcat)2(PPh3)2] (10c) and 10d along with a number of diphosphine
derivatives (10e–g), monophosphines (10h–j), or even mixed phosphines
(10k) (Scheme 7) was subsequently reported by Marder and Norman
who provided conclusive evidence about the activation of tetra(alkoxy)
diboron with Pt(0) complexes, through the oxidative addition of the
BdB bond, and further reactivity with alkynes and diynes.44,45 It is note-
worthy that the addition of 1,2-bis(dimethylphosphino)methane (dppm) to
cis-[Pt(Bcat)2(PPh3)2] proceeded to give predominantly cis-[Pt(Bcat)2(dppm)]
(10g) along with minor amounts of an unusual binuclear product [Pt2(μ-Bcat)
(Bcat)(μ-dppm)2(PPh3)] (Scheme 7). The same authors concluded that either
Pt(II)bis(boryl) or Pt(0)-ethylene complexes are more efficient catalyst precur-
sors than [Pt(PPh3)4] for the diboration of alkynes and that B2cat2 reacts
faster than B2pin2, which in turn is much faster than B2(4-Butcat)2. When
the basic phosphine PMe3 is involved in the precursor [Pt(PMe3)4], the
activation of B2cat2 takes place smoothly.46
The platinum precursor species [Pt(η2-CH2]CH2)(PPh3)2], postulated

by Smith and Iverson, hold out an inducement since the olefin ligand did not
always serve as an innocent “mask” for the low-valent metal center. In fact,
tris(bicyclo[2.2.1]heptene)platinum(0) instantaneously reacts with B2cat2 at
room temperature to give a bis(boryl)bicyclo-[2.2.l]-heptane as the chief
organic product (Scheme 8).42 It indicated that metal–olefin complexes
O O O O
B B B B
O O O O
Ph3P PPh3 Ph3P

Pt Pt
Ph3P PPh3 Ph3P
10b: B(OR)2 = Bcat

t
10c: B(OR)2 = B(4-Bu cat)
10a: B(OR)2 = Bpin
10d: B(OR)2 = B(4-X-cat)
Ph3P B(OR)2
Pt
Ph3P B(OR)2 dppm
Ph2
P Bcat
Pt
dppe P Bcat
PCy3 10e Ph2
Ph3P Bcat
Pt
Cy3P Bcat
Ph2
10k Bcat
P
Pt
PMe3 P Bcat
Ph2
PMe2Ph
10f
PhMe2P Bcat
Pt Ph2 Me2P PMe2
PhMe2P Bcat P Bcat
Pt PPh3
10j PMePh2 PEt3
P + Bcat Pt Pt
Bcat Bcat
Ph2 Me2P PMe2
10g
Ph2MeP Bcat Et3P Bcat
Pt Pt
Ph2MeP Bcat Et3P Bcat
10i 10h
Scheme 7 Multiple strategies to activate tetra(alkoxy)diboron with Pt(0) and related

transformations.
Pt
Bcat
Bcat
+
O O
B B
O O
Scheme 8 Diboration of olefins with B2cat2 by Pt(0)-olefin complexes.

Another random document with
no related content on Scribd:
beautiful. She hath consumed my soul with wild passion, mad,
unreasoning love, and he… hast seen him to-day? He is dying of the
same complaint which has sapped my manhood, made a weak
coward of the Pharaoh, the descendant of Ammoun-ra.… Hast seen
his burning eyes, his hollow cheeks? He is dying, I tell thee! he will
die in thy arms one day… soon… die of love for Neit-akrit.”
“Thou liest! thou liest! thou liest!” she shouted. “I forbid thee to
speak, thou liest!”
“He loves her, I tell thee, and thou wilt wed him to-morrow; but
he will hate thee, for his heart belongs to Neit-akrit. Ay! mother
mine, thou hast stolen my throne from me, but at least, in exchange
for that throne, I think I have succeeded in stealing from thee the
last shred of thy happiness.”
But the semi-demented creature who ruled over the kingdom of
Kamt had pursued his cruel game just a little too far. I was
absolutely helpless to intervene, even had I thought of venturing to
do so, for the heavy marble gates were between me and that
mother and son, who were hissing words of hate in one another’s
ears.
“Thou liest!” repeated the Queen, but yet she listened, as if
longing to drink to the last dregs of the poisonous cup which her son
was holding to her mouth.
“Thou art old, mother mine,” added the creature, with truly satanic
fiendishness. “Of thee he will have but thy throne. I tell thee that as
soon as he has wedded thee he will forget thy very existence: and
Neit-akrit, the divine Neit-akrit, whom I, the Pharaoh, adore, will
forget her rank, her maidenhood, and vow herself to Isis, that she
may on moonlit nights put her white arms round his neck, and show
him how well the women of Kamt have learnt how to kiss.”
With a hoarse cry Maat-kha, whose whole body seemed to
tremble with mad, uncontrolled rage, literally sprang upon her son.
With both hands she gripped him round the neck, and she held him
there, tightly clutched, before her, until perforce his evil words died,
choked within his throat. His head fell back, livid and ghastly, his
arms beat the air once or twice, while his whole being shook in a
violent convulsion.
Aghast, horror-struck, I shouted with all the force of which my
lungs were capable: I threw my body against the marble gate, only
to fall back bruised, sore and helpless. The mad woman heeded me
not; the wild mania of blind jealousy must have closed her ears. My
voice went echoing among the massive pillars of the building, but
nothing answered it save, far away, the song of the priestesses of
Isis amidst the flowers and the balmy midnight air.
The Pharaoh’s head had fallen back inert, and over him bent the
woman—his mother—still furiously hissing at the livid face beneath
her: “Thou liest! thou liest!” Then the body became rigid and still,
there was a final convulsion, the head rolled from side to side. Maat-
kha ceased her shouting; she still held the dying man by the neck,
but her eyes, now large and terrified, were fastened upon him.
Gradually a look of indescribable horror spread over her face, a look
which almost froze the blood in my veins, so appalling was it. The
momentary mania had disappeared and in its stead came the terrible
realisation of what she had done. Again I shouted to her to let me
in, but she seemed not to hear, for she did not even turn towards
me, though I screamed myself absolutely hoarse. For one moment I
thought of turning towards the garden and shouting for help in that
direction, then the idea of Hugh hearing my voice, of seeing what I
had seen without warning or preparation, struck me with
unspeakable horror, and stupidly, unreasoningly, I threw myself
again with all my might against the stone gate, hoping to attract
some attention.
I must have done it very clumsily, for I caught my head a nasty
blow which stunned me for a moment, and, half-unconscious, I fell
down on my knees against the gate.
CHAPTER XXIV.
THE ALTERNATIVE
When I came to myself after a few minutes, the scene inside the
temple had changed. The Pharaoh was lying rigid upon the marble
floor and the hanging lamp overhead threw a weird, flickering light
upon his livid, hideously distorted face. Beside him, ghastly pale,
with eyes staring full of horror upon the dead body of her son,
Queen Maat-kha stood silent, with arms folded across her bosom,
her lips tightly set. She was listening to the high priest of Ra, who
was speaking to her in slow and solemn tones, while he pointed
upwards to the sanctuary of the goddess.
“Thy sin, Maat-kha, is beyond forgiveness. Thou knowest it; thy
body and thy soul are doomed to eternal death. Thy very memory
will be accursed in Kamt as the centuries roll slowly away.”
She did not reply. I think she was absolutely dazed. No doubt that
even a British jury would have found extenuating circumstances for
her crime. She had been provoked beyond what her reason could
stand. Momentarily it had fled, escaped her body, leaving her a prey
to all the furious passions which her maddened jealousy had roused
within her. Now reason had returned, and with it horror, repulsion,
and hideous, terrible remorse.
I was still very shaky on my legs, and somehow instinct kept me
where I was, waiting to see the sequel to this awful and weird
tragedy. There was dead silence after the high priest had spoken,
and the echo of his last solemn words still reverberated in the vast
and mysterious temple. From afar the last sounds of life and bustle
from the bridal city reached this lonely, poetic spot only as a murmur
from dreamland.
Maat-kha stood as rigid and inert as her dead son, only from time
to time a nervous shiver went right through her, and she gathered
her veil close to her as if she felt cold.
“I am waiting for thy answer, Maat-kha,” said the high priest.
She looked up at him, half-appealing, half-defiant. There was no
sorrow on her face for the dead son whom she had never loved, no
fear of the punishment with which the high priest threatened her.
She said very quietly:
“What answer dost thou expect of me?”
“I wish to know if, after thy madness, thou dost understand the
hideousness of thy crime, and dost fear the vengeance of the
goddess whose temple thou didst desecrate?”
“My hands did act, but not my will. He taunted me and my reason
fled. I had no wish to kill him, only to silence his poisonous tongue.”
“Hold thy peace, woman! Do not slander the dead and heap more
sorrow and humiliation upon thy doomed head.”
“What wouldst thou have me do, Ur-tasen? Madness seized me. I
am accursed. Wilt thou give me the boon of a dagger with which to
send my sinful soul to the foot of the throne of Osiris? who perhaps
will understand, and understanding, pardon.”
“Thy soul is not worthy to appear before the gods. Judgment
would decree that thy body be allowed to rot, lest so vile a soul find
once more habitation upon earth and live to commit other most
horrible crimes.”
A shudder went through her; for the first time she seemed to
realise that some awful punishment would inevitably follow her sin.
She looked wildly round her as if in search of help or sympathy, then
again appealingly at the high priest before her.
“There is no help for thee, woman. Look not around. The very
walls of the temple of Isis frown shuddering down upon thee. Nay!
look not for help, for not even he, whom thou deemest all-powerful,
could save thee if he would.”
The words of Ur-tasen recalled me to myself. I realised that in a
moment the whole aspect of Hugh’s future had changed, and it was
but just that he should be apprised of the tragedy which had taken
place, and of the awful doom which suddenly threatened Queen
Maat-kha. There was no object in my staying here any longer to
hear Ur-tasen’s solemn invectives against the unfortunate woman,
and I had almost turned to go, when it seemed to me that in the
remote corner of the temple, behind Queen Maat-kha, there was
some one standing and like myself watching the weird and terrible
scene. I could only see a dim outline thrown darkly against the light
curtain, but somehow that outline, the heavy hair, the quaint,
straight attitude, forcibly reminded me of Princess Neit-akrit.
Surely I was mistaken. What could Neit-akrit be doing alone at
night in the temple of Isis? and why should she have stood
motionless and still while so awful a tragedy was being enacted
before her? And yet, persistently I looked at the slight and upright
figure and continued my rôle of eavesdropping, scenting vaguely
danger hovering in the air.
At mention of Hugh’s name Maat-kha had closed her eyes. A look
of infinite pain spread over her face, and slowly two heavy tears
rolled down her cheeks.
But Ur-tasen was merciless.
“How he will loathe thee, Maat-kha,” he said very quietly. “Hast
thought of that? He never loved thee dearly: thy beauty had not
even the power to ensnare his senses, but I think he honoured thee
as a woman and as a queen: whereas now he will turn from thee as
from a noisome reptile. With his own hand he will sign the decree
which will cast thee out of Kamt, and as thy flesh begins to wither
on thy bones, out there in the valley of death, thy dying soul can
contemplate the picture of happy, prosperous Kamt, wherein the
stranger, the well-beloved of the gods, dispenses justice and wisdom
beside Neit-akrit of the house of Usem-ra.”
A prolonged moan of anguish escaped the unfortunate woman’s
lips: she turned to the high priest and very calmly she asked:
“Ur-tasen, why dost thou put this torture to my soul? Speak! What
dost thou want of me?”
“I but want the salvation of thy soul, Maat-kha, seeing how
grievously thou hast sinned. I but wish to adjure thee to think of the
vengeance of the gods.”
“I will think of that by-and-by,” she said, “now…”
“Now thou dost think only of what thou hast lost and what Neit-
akrit has gained.”
“No, no, no, no! Ur-tasen, no! thou dost not know of what thou
speakest. See! I will drag myself on my knees before thee. I will
weep both my eyes out for repentance! I will go forth into the valley
of death cheerfully and calmly, accepting thy decrees and blessing
thy name. I will cause all my wealth, my jewels, my palaces to be
left to thee, as thine own property, when I am gone, if thou wilt part
my lover and Neit-akrit for ever.”
She had sunk down upon her knees, and laying her pale forehead
on the marble floor before the high priest, she beat the ground with
her head and kissed the tip of his pointed sandals. I thought the
high priest’s face suddenly assumed a satisfied, triumphant
expression. He folded his arms across his chest and looked down
upon the suppliant at his feet.
“Wilt come up before the image of the goddess, oh, Maat-kha!
and at her very feet swear that thou wilt do my bidding, whatsoever
I might command?”
She raised her head, and in the dim, flickering light I could see
that she darted an inquiring, amazed look upwards at him.
“Dost believe that I am powerful?” he asked.
“I believe that thou dost hate him who is beloved of the gods.”
“Wilt swear to do my bidding?” he repeated.
“Dost wish to harm him?”
“Not unless thou also dost wish it.”
“I love him, Ur-tasen,” she said in truly heart-rending tones.
“Wouldst see him then in the arms of Neit-akrit?”
“I would sooner see him dead at my feet,” she replied, with
renewed passion, “slain by my hands, as was my son, the Pharaoh.”
“Swear to do my bidding, Maat-kha, and Neit-akrit will never wed
the stranger king.”
She rose slowly to her feet and turned towards the sanctuary of
the goddess.
“Lead the way, Ur-tasen,” she said with absolute calm. “I will
swear to do thy bidding.”
The sanctuary was at the farther end of the building. Already the
high priest, followed by Maat-kha, was rapidly disappearing in the
vastness of the temple. Helpless, I looked round me. The conviction
had gradually forced itself upon my mind that Ur-tasen
“I will cause all my wealth,… to be left to thee,… if thou wilt part my
lover and Neit-akrit forever”
had concocted some evil plan against Hugh, for which he required
the co-operation of the Queen. Her terrible unpremeditated act had
given him an enormous power over her, and, working upon her mad
jealousy, he meant evidently to make her his ally in his nefarious
scheme. At any cost I was bound to hear what that man and that
woman would say to one another during the next few minutes, and
there was the whole length of a vast temple and the thickness of
marble gates between me and them. On the floor, beneath the lamp,
the livid mask of the dead Pharaoh seemed to grin at my
helplessness. It seemed as if, dead, he would be able to wreak that
vengeance upon the man he hated which, living, he had never dared
accomplish.
Already I could see Maat-kha prostrate before the goddess, with
arms stretched upwards, swearing no doubt to add another deadly
sin to her crime, and in Ur-tasen’s attitude, standing erect and
commanding by her side, there was an unmistakable air of exultant
triumph.
There was no question that, from where I was, there could not be
the slightest chance of my hearing what those two said. Certain of
not being watched, determined to know the extent of the projected
evil before I warned Hugh of his danger, I thought of rapidly skirting
the temple walls, in the hope of finding some other gate or entrance
nearer to the sanctuary from whence I could watch and listen. The
precincts of the temple were absolutely deserted, as far as I could
see, and, in any case, my feet were shoeless, and the shadows
between the pillars were long and dense. I had every chance of
slipping round unperceived.
I made slow and very cautious progress. The temple was vast and
it took me two or three minutes’ measured creeping before I
reached its more distant side. As I had hoped, another gateway, also
of marble tracery, led into this part of the temple, and to my delight
I found that this gateway was opened sufficiently to allow me to slip
inside, which I did.
I found myself, however, not in the temple itself, but in a kind of
chamber or passage, I did not know which, for it was very dark.
Some five feet from the ground a narrow opening, scarce the width
of an arm, in the granite wall, showed beyond it the brilliantly-
lighted sanctuary. At first, in looking through this aperture, I could
scarcely see, for the dazzling brightness of the innumerable hanging
lamps, and the thick fumes of burning herbs, shut everything out
from my view. But gradually, as my anxious gaze travelled round, I
saw Ur-tasen and Maat-kha not ten feet away from me to my left;
but the gossamer curtain hung between the sanctuary and them,
and I could only vaguely distinguish their forms. Beyond them I
could see nothing but gloom; the dim shadow, which I had fancied
to be Princess Neit-akrit, had apparently disappeared, if indeed it
had ever been there, and the high priest and the Queen evidently
thought themselves alone.
“He often used to evade his attendants at nighttime,” Maat-kha
was saying, apparently in answer to a query from the priest, “and
wander about aimlessly in the gardens or the palace. I had come
into the temple to pray, bidding my women go and leave me in
peace for an hour, when suddenly I saw the Pharaoh before me.”
“I know the rest, for I saw and heard all,” replied the high priest,
quietly.
“And thou didst not move a finger to save him from death, and thy
Queen from a crime ten thousand times worse than any torment?”
she exclaimed with a smothered shriek.
“The will of the gods is inscrutable,” he replied calmly. “I am but a
servant of all-creating Ra. ’Tis he ordered me to be silent when the
holy Pharaoh fell smitten by his mother’s hand. His will must guide
thee, too. Thou hast sworn to do my bidding.”
“I will obey,” she said very meekly.
“Listen then to the commands of Ra, of Osiris, and of Horus, of
Set, and of Anubis and all the gods in Kamt, whose wrath, if thou
disobey, will fall heavily upon thy criminal head. I command thee to
go anon, when thy women come to attend upon thee, back to thy
palace peacefully and silently. The priests of Ra will guard the body
of the Pharaoh until such time as the soulless corpse will have
helped to fulfil the deed of vengeance which the gods of Kamt have
decreed.”
“I do not understand.”
“Listen, Maat-kha,” said Ur-tasen, more eagerly, as he bent his
shaven crown close to her ear; “at the midnight hour, when Isis is
high in the heavens, the stranger, who with sacrilegious arrogance
doth style himself beloved of the gods, will plight his troth to thee.
Ignorant of thy terrible crime, he will swear that he will love and be
true to thee, and reverence thee as men of Kamt do reverence the
wife whom Isis places in their arms. Do thou be silent and at peace
—none but I have seen the evil midnight deed—do thou be silent
and at peace, and place thy hand in that of the stranger.”
There was a pause, while I pictured to myself the unfortunate
Maat-kha listening to the priest’s commands, not daring to cling to
the thin thread of hope which he was so enigmatically holding out to
her.
“After the solemn marriage ceremony,” resumed Ur-tasen, “by the
custom of our beloved land, the royal bridegroom remains in the
temple of Isis, waiting and alone. All those who have come bidden to
the feast retire to their homes, to ponder of what they have seen, or
to join the populace in their revelry in honour of the joyous night.
But the royal bridegroom waits in solitude and prayer; waits until his
bride is ready to receive him, at the first streak of dawn, when Isis
herself sinks fainting into the arms of Osiris her beloved, and
suffuses the vault of heaven with the roseate hue of her bridal blush.
Then the royal bridegroom goes forth to meet his bride, and his
footsteps lead him through the garden of Isis to that secluded nook,
beside the sacred cataract, where stands the hallowed shrine of the
goddess, and where foot of man ne’er treads, save he be of royal
blood, and hath not yet received the first kiss of his bride. Dost
remember the spot, oh, Maat-kha?” he added. “There didst thou go
twenty years ago, one summer night, beneath the light of sinking
Isis; there didst thou hear the sound of the path crunch beneath the
foot of Hor-tep-ra; there didst thou give the first bridal kiss to him
whose son thou hast murdered, within the very temple of the
goddess.”
“I remember,” she murmured dreamily, “and oh! how oft have I
not thought of that solemn meeting within the sacred precincts, with
him whom I love beyond all things earthly—with him who to me, to
all Kamt, is sacred, nay! divine.”
“It will not be thou, oh, Maat-kha! who wilt meet the bridegroom
beneath the shrine of Isis.”
“Who then, oh, mighty priest of Ra?” she asked with sudden
terror.
“The dead body of thy murdered son.”
“I do not understand.”
“Nay! thy mind must be strangely overclouded. The Pharaoh did
oft in his life evade his attendants and wander about aimlessly in his
palaces and his gardens. To-night, more sick than ever, he found his
way to the precincts of the temple of Isis, but faintness overtook him
—faintness so great that the priests of the goddess laid him on a
couch within the sacred building and tended him with loving care.
But he is too sick to attend the wedding festivities, and the priests of
Isis will have charge of him while Tanis goes raving mad with joy.
Tanis will forget the sick Pharaoh in her tumultuous happiness, and
those few who will remember him will know that the holy monarch is
well cared for by the most learned in the land.”
I confess that not even then did I really understand the devilish
plan which the high priest of Ra had conceived. That it was in some
way to encompass Hugh’s ruin was of course evident, but what
connection the dead Pharaoh was to have with it, or the mysterious
and poetic retreat by the cataract, I could not as yet imagine. The
Queen, too, was evidently as much at sea as I was, for she repeated
mechanically:
“My mind is dull, Ur-tasen. Still I do not understand.”
“During the joyous ceremony,” continued the high priest, “the sick
Pharaoh again evades his thoughtful guardians, as he often has
evaded his attendants, and his roaming footsteps lead him to the
waters of the sacred cataract, the secluded spot wherein the royal
scions of ancient Kamt whisper first of love and home. The shrine of
the goddess is enclosed by high walls shut off by copper gates;
these are never opened save on glorious nights—like to-night will be
when the widow of Hor-tep-ra will await her stranger lord. But the
holy Pharaoh, finding the sacred grove still deserted, doth lay
himself there to rest…”
The high priest paused, then added, in a whisper so low that I
could hardly hear:
“He who calls himself beloved of the gods hath no love for the sick
Pharaoh, who stands between him and absolute power.… The night
is lonely… the gardens silent… and the Pharaoh helpless. The
stranger has the strength of a lion… the strength which breaks the
golden wand of the high priest of Ra with one touch of the hand…
and which smothers the last cries of a dying man as easily as the
carrion of the wilderness devour their prey…”
“Thou wouldst…”
“I would break the might of him who has ensnared the people of
Kamt and broken their allegiance.… The priests of Isis will softly
follow in the wake of the stranger, as he turns his footsteps within
the hallowed nook.… Horror-struck, they will see the murderer
standing beside his victim, then they will loudly call upon the people
of Kamt to quit their rejoicings, to forget their songs and laughter
and behold the hideous crime committed by him who dared to call
himself the son of Ra!”
“Ur-tasen!” shouted the Queen, appalled at the hideousness of so
vile a plot.
But I did not wait to hear more—cared not to hear how the man
of evil, that cowardly, treacherous priest, succeeded in forcing the
unfortunate, criminal woman’s will. My only thought was to fly to
Hugh, to warn him of the base plots which threatened him, of the
villainy of the woman to whom he had all but pledged his troth.
Thank God! that monstrous oath had not yet been spoken, and my
friend Hugh Tankerville had not, by any pagan ritual, sworn to love a
murderess. Thank God!—our God—who led my footsteps to this
idolatrous temple to-night, whereby I was allowed to see and hear,
and warn Hugh in time.
“If thou refuse,” I heard finally Ur-tasen saying in threatening
accents; then he paused, and added with a touch of satire, “Thou
art still at liberty to refuse, Maat-kha, to break the oath thou didst
swear just now. The body of thy murdered son still lies there, and I,
the high priest, can yet summon the people of Tanis and show them
their criminal Queen, she who then, to-morrow, will be for ever cast
out of Kamt, a prey to the jackals and vultures, while in Tanis the
wedding festivities will not even have been put off for so trifling a
matter, seeing that the beloved of the gods, the son of Ra, will still
be there, ready to wed Neit-akrit of the house of Usem-ra. Ay! thou
canst still refuse, and think, when the gates of Kamt are shut for
ever upon thee, of that same nook beside the sacred cataract, where
the stranger will wait for the beautiful princess with the ardent hair
and the eyes as blue as the waters of the lake; surely these will soon
help him to forget the erstwhile Queen, the criminal, murderous
Maat-kha.”
I knew that she would give in, of course. Her love for Hugh was a
barbaric, sensuous one, which would ten thousand times prefer to
see the loved one dead than happy in another’s arms. There was no
object in my listening any further. The plot was hideously vile and
treacherous, and perfectly well-conceived. I shuddered as I thought
of what might have happened had not divine Providence led me
here.
It did not need much reflection as to what I should do. My first
impulse had been to go to the top of the temple steps and there to
shout until I had assembled the people of Tanis round me, and then
to show them the dead body of the Pharaoh, its murderess and her
accomplice. In any case I had not many minutes before me, as
undoubtedly in the next few moments Maat-kha would give in and
Ur-tasen would order the dead body to be removed.
I went back to the gateway through which I had slipped into this
chamber not a quarter of an hour ago… it was shut.
That was strange! I tried to find the opening… impossible to move
the gates.… I only succeeded in bruising my hands and smashing my
nails. The gate was of solid marble, the tracery a foot thick. It was
obviously childish to attempt to force it open. As for any sign of lock
or hinge, I certainly could see none. These Egyptians have secret
springs to every door that leads to their temples.… Moreover, it was
pitch dark all round me. Only between the carving the brilliant
moonlight came weirdly creeping through.
CHAPTER XXV.
HELPLESS
It was obvious that from that side I was an absolute prisoner—

temporarily, I hoped—but minutes, even seconds, were valuable.
From the temple I could hear Ur-tasen’s voice:
“For the third and last time I ask of thee, woman, wilt thou obey
the decrees of the gods, or art thou ready to face the awful doom
which thy loathsome crime has brought upon thee? Thy death and
thy disgrace, or his?… which?… Dost love the stranger so dearly,
then, that thou wouldst see him happy in the arms of Neit-akrit with
thy crown upon her head?”
And Maat-kha’s voice, low and calm:
“I will obey, Ur-tasen!”
I returned to the aperture from whence I had watched the two
evil conspirators. It was no wider than my arm, and from there I
could have done nothing but shout, which obviously would have
been worse than foolish. I felt not unlike a caged beast, for although
I had not as yet the slightest fear of not being able to warn Hugh in
time, nevertheless there was no doubt that my position was, to say
the least of it, a precarious one, and that I could in no case do
anything summarily to expose the murderous plotters.
From where I was I could not see the body of the Pharaoh, and
now Queen Maat-kha, with head bent, was walking away towards
the farther end of the temple, while the high priest remained
standing before the sanctuary of his own pagan goddess, with arms
outstretched, murmuring some heathen prayer.
There was long and deathlike silence in the great edifice. Maat-
kha had probably gone, taking her conscience with her—if indeed
she had any; the high priest had finished muttering his prayers, and
I watched—like a caged beast—Hugh’s deadly enemy exulting over
his anticipated triumph. I would not allow myself to reflect over the
deadly peril of my position. My only thought was one of horror for
the diabolical cunning of the plot, which apparently stood such a
good chance of success. For the woman I had more of pity than of
loathing or contempt. The high priest, with wonderful art, had
known how to touch and play upon every sensitive and quivering
chord of a highly passionate nature, had with sagacious dexterity
roused every jealous instinct in her heart, until, blinded by her own
passions, she had given herself over, body and soul, to his guidance.
No!—I don’t think I reflected much upon my own danger. When
thoughts of it rushed across my mind, I succeeded in speedily
dismissing them. I could not do with such thoughts, for all must tend
towards the future, upon how best I could save both my friend and
myself. I cursed my own folly, my dilatoriness, the stupid way in
which I had allowed myself to be trapped. How long I should remain
merely a prisoner I could not of course conjecture, nor did I know
whether my precarious position was the result of design or accident.
At the marriage ceremony Hugh would face the sanctuary, in the
centre of the building, more than a hundred feet away from where I
was, and probably with the gauze curtain between me and him, but
I trusted to my lung power and to his presence of mind… if… I was
left alive until then.
In the meanwhile I could do nothing but watch. Several attempts
at pushing open the gateway had convinced me of their futility. Ur-
tasen had been standing immovably for some time before the
goddess, and I could see his shaven crown, which hid so many evil
thoughts, shining behind the silvery curtain. Many absolutely British
sentiments and desires with regard to the old beast made me gnash
my teeth in my impotence, and even mutter several fine words, as
with head erect he seemed to exult over his coming triumph. I
supposed that as he stood there he was seeing visions of the
stranger being comfortably cast out of Kamt, and of turning in the
wilderness to human flesh and blood for final, loathsome food and
drink.
Suddenly, as I looked, it seemed to me that Ur-tasen was no
longer alone, but that there stood beside him the same quaint and
rigid form which already before, in the gloom, I had thought that I
recognised. It was but faintly outlined beyond the folds of the gauzy
tissue, and I did not know if my tired eyes were not beginning to
play me a few tricks, when Ur-tasen turned and spoke, in a humble
and almost tender voice, so different to that in which he had
addressed the unfortunate Maat-kha:
“I did it all for thee, Neit-akrit!”
Then I knew that I had not been mistaken. She was there, had
probably seen and heard as much of the awful scene as I had, and
had not made a movement to save her kinsman or to denounce his
murderess. I recollected my old-standing distrust of her, and yet,
remembering how young and beautiful she was, I could not admit to
myself that she could approve or in any way be accessory to the
hideous treachery. She had not replied to the high priest’s words,
and he continued eagerly:
“I bless the goddess who led me to her temple to-night, who
whispered to me that I should watch the sick Pharaoh, as he
noiselessly crept up through the sacred building and disturbed his
mother in her devotions. I praise the goddess, Neit-akrit, who with
one terrible blow doth allow me to sweep from thy path all those
who dared to stand between thee and the throne of Kamt.”
I don’t know if Neit-akrit made any reply; certainly, if she did, it
must have been in a whisper, for I did not hear. Then the high priest
repeated, with accents that were soft and pleading:
“I did it all for thee, Neit-akrit, that thou mightest wear the double
crown of Kamt, and that thine enemy might be driven forth from the
land, where, in his arrogance, he dared to lay hands upon thy
throne.”
“My enemy?”
Her voice came as a murmur, sweet and low: the words spoken
half in astonishment, half in a strange and tender appeal.
“Ay!” said Ur-tasen, vehemently. “Thy throne is free now, Neit-
akrit: I have cleared the way for thee. Maat-kha struck her dying son
with wrathful arm; I did naught to save him, for by that blow thy
kinswoman delivered herself and her stranger lover into my hands.
At dawn, anon, when Isis has sunk to rest, he who has dared to call
himself the son of Ra will go forth to his doom. Think of it, Neit-
akrit! He, alone with the dead body of the Pharaoh! the opening of
the gates! the call of the priests of Isis! the rushing of the mob! the
shouts of joy transformed into cries of execration at the hideousness
of the crime! Then think of it, Neit-akrit! think of the judgment day,
when thine enemy, he who had thought to place himself upon thy
throne, is led forth bound hand and foot with ropes, humble—an
abject criminal—within the great hall of Men-ne-fer, there, on the
very spot where thy slave Kesh-ta died, slain by his hand, so that
she might escape the just and awful punishment of her crime, he—
the son of Ra—will stand, and as the priests of Isis, one by one, with
loud voice, will accuse him of the murder of the holy Pharaoh, one
by one the lotus blossoms will drop out of the hands of the judges,
and I, Ur-tasen, will pronounce judgment upon him. Then, after that
—in the early morning…”
The bald old reprobate was evidently enjoying himself amazingly
over the recapitulation of all he had prepared for Hugh, but here,
suddenly, Neit-akrit interrupted him, and her voice sounded curiously
hard and calm.
“And hast no fear, Ur-tasen, that after that, in the early morning,
the very gods will arise and kindle the flames of heaven and hurl
down the mountains and the rocks over Kamt, in order to bury her
and her shame?”
“I do not understand thee,” said the high priest, amazed. “Why
speakest thou of shame?”
“Because already I see thy hands stained with his blood, and my
very soul turneth in abhorrence from thee.”
“Nay, Neit-akrit! his blood shall not stain the soil of Kamt; the
vultures of the wilderness alone will see if it be red. Remember, thy
kinsman, the holy Pharaoh, died because his mother felt that he was
the stranger’s enemy. Remember that he set himself upon the
throne of Kamt, which by right should be thine. Remember…”
“I remember,” she interrupted again, speaking slowly and
dreamily, “that he came to us and visited Kamt. He said he came
from the foot of the throne of Osiris: well! that is as it may be;
surely he is so good to look upon that some of the gods must have
lent him their radiance. He came, and the people of Kamt were
joyful, and in all the land, since he came, there has been one long
and uninterrupted festival. He came, and put a check upon thy
cruelty, when thou wouldst have sent a half-crazy woman to die of
slow torture in the valley of death. He spoke to thee, and to all the
judges of Kamt, of justice and of mercy. He came and we all found
him fair, and we rejoiced and loved him, and kissed the ground
before his feet. He made us all happy, and we waited all these days,
then repaid him with treachery.”
“Neit-akrit!…” protested the high priest.
“Nay! do not speak! I must have my say. I will not hear it again,
that thou dost these evil things for me. I did not see Maat-kha’s
hand raised against her son: when I came into the temple, alone
and unattended save by Sen-tur, the Pharaoh was lying livid upon
the ground, and his mother had begun to feel the first pangs of
remorse. This I swear by Isis herself, and thou knowest, Ur-tasen,
that I never lie. But I saw thee, standing exultant in the gloom, and
somehow I knew that thy thoughts were evil. I did not denounce the
vile murderess, even while she bent red-handed over the body of
her son, but I waited and listened: I heard thy treachery, thy
cowardly plan, and that is why, Ur-tasen, I speak of shame to thee!”
She spoke very quietly, in that same monotonous, sing-song way
which is the inalienable characteristic of this most ancient language.
Ur-tasen, I think, was completely taken aback by her unexpected
defence of Hugh, and probably the first inkling that she might prove
his enemy instead of that of the stranger penetrated into his
scheming mind. I, from where I watched, felt a sudden wave of
hope sweep over me, and of remorse for the wrong I had done the
beautiful girl by suspecting her in my thoughts. I experienced an
overwhelming desire to shout a triumphant shout at our enemy, for I
felt that in Neit-akrit now I should have a powerful ally.
There had been a long pause after the Princess had finished
speaking. I imagine that old brute was meditating as to what his
next tactics should be. At last he said very calmly:
“Thou speakest with wondrous ardour, Neit-akrit. Hath the
handsome presence of the stranger made thee forget that he has
usurped thy crown? The gods commanded me to act as I did act, to
hold my peace whilst Maat-kha and the holy Pharaoh fought out
their last and deathly quarrel, and to speak their decrees to the
murderess when tardy remorse had at last penetrated her soul.”
“Nay, Ur-tasen!” she said, “blaspheme not, and take not the name
of the gods of Kamt in so unholy a cause!”
“Who art thou, girl,” thundered the high priest in his most
commanding accents, “who darest to upbraid the high priest of the
Creator?”
“I, Neit-akrit, Princess of Kamt,” she replied proudly, “I, who dare
to stand here and defy thee. Defy thee to do thy worst.… Ay! thou
comest here in the temple of Isis, and in the guise of thy high and
solemn priesthood thou lendest thy hand, thy mind, both of which
thou hast vowed to the service of the gods, to a deed so base and
dark that, methinks, Osiris will not rise to-morrow beyond the hills of
Kamt, lest the very atmosphere, through which penetrate his golden
rays, be polluted by thy treachery. Nay! prate not to me again thy
thrice-told tale that thou didst so monstrous a thing for me! I tell
thee, man, that Neit-akrit’s foot would never ascend the steps of a
throne rendered slippery with blood, but that her first act of justice
in this land, since Maat-kha its Queen has forfeited life and crown by
her unholy deed, will be to denounce thee and thy accomplice
before the people, and for ever crush that power which thou darest
to measure against the beloved of the gods.”
Thank God, and all his saints, the beautiful girl was proving true!
It mattered not now whether I was free or a prisoner. Hugh, in any
case, was out of danger, and my deliverance would follow in natural
sequence; already I was sending up a prayer of heartfelt gratitude to
Him who rules all our destinies, and indulging in less Christian-like
sentiments with regard to the discomfited foe, when his loud and
derisive laughter suddenly dispelled these first glimpses of hope.
“Ha! ha! ha! Neit-akrit, Princess of Kamt! How strange and
laughable are thy thoughts! Didst really think thou couldst pit thy
woman’s wit against that of him who has for thirty years guided the
destinies of Kamt? Wouldst denounce him, dost thou say? To whom,
fair Princess? and for what? Hast strength to wield the mighty
clapper which calls the people of Tanis to the temple, or might to
shriek that those same people, mad, blind and deaf with joy, should
hear, and, hearing, come rushing to the sanctuary of Isis to find—
what? The dead body of a murdered Pharaoh? Where is it?… The
holy Pharaoh is sick, and in the inner precincts of the temple, to
which his footsteps led him, ailing and wandering… the priests of Isis
are busy lavishing their skill and care upon him. There are twenty of
these within my call now, who are ready to swear to the people of
Kamt that, though sick, the Pharaoh lives.… And the people of Kamt,
who left their rejoicings in answer to the wild shrieks of a woman,
will return to their homes, their dancing and their music, with a
puzzled and perhaps sad shake of the head, saying, ‘Princess Neit-
akrit, of the house of Usem-ra, the beautiful, is no longer pure;
madness has caused her tongue to lie, at the very foot of the throne
of Isis, desecrating the temple of the goddess.’ And some, no doubt,
with a shrug will add: ‘Madness which cometh of love for the
stranger, unhappy love for him who will have none of her, since he
will wed Maat-kha, anon.’ ”
“Hold thy peace, Ur-tasen. I forbid thee to speak of these things.”
“Nay! I will not hold my peace, Neit-akrit, Princess of Kamt, thou
who didst dare say that thou wouldst defy me! Didst think that it
were so easy to circumvent the plans of Ur-tasen, the high priest of
Ra? Didst think I should allow thy girlish sentiments to upset what I
have thought and dreamed of ever since the stranger has usurped
my power? Go and strike the metal gong, Neit-akrit, go and summon
the people of Tanis. Derision and contempt await thee, and thou wilt
not help the stranger withal.”
Then, as she did not reply, but stood like an image of deep
thought, with her golden head bent, he added:
“Hadst thou reflected, when thou didst venture to threaten and
upbraid me, that thou wast within the precincts of a temple of Kamt,
that in every nook, every corner of the gigantic building, the priests
of Isis, and those of Ra, those of Horus and those of Osiris, are
there lurking ready to answer the high priest’s beck and call? Go up
the steps, Neit-akrit, which lead to the ponderous gong, take the
mighty clapper in both thy hands, and I tell thee that before metal
touches metal thou and thy soul will have fled to a land whence thou
canst not return to thwart the will of the high priest of Ra, and a
memory of something young and beautiful, the remembrance of a
lock of golden hair, will be all that will remain in the land of Neit-
akrit, Princess of Kamt.”
I was glad that he had chosen to give this timely warning to the
Princess, for I personally had been ready to shout to her, signifying
my presence, and trusting to her wit and power to get me out of my
difficult position. The mention of a host of shaven priests, hidden I
knew not where, threw cold water upon my ardour, and I gnashed
my teeth lest my British temper should get the better of me, and lest
through the bars of my prison I should be impelled to hurl an
ineffectual, if to me convincing, malediction against the
unscrupulous and treacherous blackguard who was hemming us in
all round.
“It was because I knew this, Ur-tasen, that I did not shout to the
people of Kamt the moment I saw the murderous deed and realised
the blackness of thy treachery,” said Neit-akrit, quietly. “I did not see
the Pharaoh die. I came into the temple alone at the very moment
when his body, after a final convulsion, rolled rigid upon the floor.
Then I caught sight of thee; the flickering light of the lamp illumined
thy face, and I knew that thy thoughts were evil. Silently I waited
and listened; heard of thy villainy and Maat-kha’s weakness, and
trusted to the gods to give power to my words, to turn thee from the
dark path, before it be too late.”
I thought that she looked round her as if realising for the first time
the loneliness of her position. Certainly these last few words showed
decided signs of coming weakness, and my awakening hopes began
to give way to a creeping feeling of disappointment. She was, of
course, entirely at the mercy of an unscrupulous and daring man,
whose sacred office gave him every power and opportunity of
suppressing, temporarily or permanently, every inconvenient enemy.
Personally, I thought that his last threat had been a bluff; he would
surely not have dared to put Princess Neit-akrit entirely out of the
way at the same time as the Pharaoh. She was the idol of the male
population of Kamt, and suspicion might perhaps fasten
uncomfortably upon the high priest and his deacons. At the same
time, undoubtedly, Neit-akrit’s life was doubly precious if she really
meant to help Hugh. The question which agitated my mind was,
Would she care to thwart the high priest, at risk of some terrible
retaliation on his part? Of course I did not understand her nature.
How could I, a prosy Britisher, read the thoughts and feelings of so
curious and ardent a temperament? Some time ago I had mistrusted
her; then, a curious jealous feeling, of which I am heartily ashamed,
made me turn against her when I saw how completely she had
taken possession of Hugh’s heart. Both these feelings had in their
turn overclouded my brain as to her real character, and I really was
no judge as to whether she hated Hugh as a usurper, or if she cared
for him. She was impulsive and capricious, sensuous and ardent,
that I knew. Perhaps it had been mere impulse which had dictated to
her to admonish, threaten and warn Ur-tasen, and to save Hugh if
she could; that impulse had perhaps died out again, and visions of
the throne rendered vacant for her by the Pharaoh’s, Maat-kha’s and
ultimately Hugh’s death, chased nobler thoughts away from her
mind. She did not speak for a long time, and Ur-tasen stood and
watched her with arms folded across his chest, his whole attitude
one of scorn and command.
“The hours slip by, Neit-akrit, on the winged feet of time,” he said
with pronounced sarcasm. “Hast forgotten that within the next two
hours the emissary of Osiris, the son of Ra, he who hath made us all
happy and rejoicing, will wed Maat-kha our Queen, the widow of
Hor-tep-ra? Hast forgotten that at the marriage ceremony, amidst all
that are there, among all those who are fair in the land, there must
be one who is fairer than all? Thy women await thee, no doubt,
ready to deck thee with the snow-white robes which befit thy beauty
and thy innocence. Nay!” he added with sudden softness, “thou art
beautiful above all the daughters of Kamt, the perfume of thy hair
sends delicious intoxication even through my shrivelled old body.
Thou art fair, so fair that I would fain see the double crown of Kamt
upon thine ardent hair. To accomplish this I plotted and I planned.
Thou art a child and dost not understand. Leave thy destiny, the
destinies of Kamt, in the hands of him whose firm will can guide
them. Believe me, if in return thou wilt but smile on him and tell him
thou art satisfied, he will be content.”
She did not reply, and he added pleadingly:
“I did it for thee, Neit-akrit! In order that I with mine own hands
might place the crown of Kamt upon thy golden hair, in order that
none should rule over thee, that thou shouldst be queen indeed, as
thou art queen only by thy beauty and by thy smiles. Tell me, art
satisfied?”
And very quietly she answered:
“I am satisfied!”
I could scarcely believe my ears. Disappointment was so
overwhelming that I almost shrieked with the agony of it. Already
she had thrown up the sponge. Ambition had quickly swept aside
the noble impulse which had made her plead for Hugh. And again
Ur-tasen was triumphant, and I, helpless, left once more, after a
brief ray of hope, in an uncertainty which was now still harder to
bear.
“Before thou goest, Neit-akrit,” said Ur-tasen, “I would have thee
swear to me that neither by look nor word wilt thou betray to any
one the plans of the high priest of Ra.”
But Neit-akrit was silent; and Ur-tasen added quietly:
“Nay! perhaps thou needest not swear. An oath can so easily be
broken, in the spirit if not in the letter. I think I can trust thee best
when I say that, shouldst thou before dawn anon think of warning
the stranger of what awaits him in the nook beside the sacred
cataract, and his footsteps should not in consequence lead him
thither, then, of course, no obstacle will stand between the beloved
of the gods and Maat-kha, his bride. The priests of Isis, after the
first hour of dawn, will take the body of the holy Pharaoh back into
his palace, and swear that he died of sickness in his bed. Then the
happy union can be consummated, and thou, Neit-akrit, the
defrauded Princess of Kamt, canst in thy unselfish joy watch the
happiness of Maat-kha, the murderess, in the arms of her beloved,
the son of Ra, loved of all the gods: and I can swear to thee that he
shall not know that the wife of his bosom is the murderess of her
first-born until she hath borne him a son, the heir to all her vices.
Farewell, Neit-akrit, future queen of Kamt!”
Oh! he was a cunning brute, was old Ur-tasen: again he had put
his finger upon the most vulnerable spot in any female armour.
Death to the loved one or his happiness in another woman’s arms:
the great problem which has torn passionate women’s hearts in
every country and beneath every clime, since the world began. Oh!
that I could have read in Neit-akrit’s heart and known what she
would do! How far and in what way did she care for Hugh? The
alternatives seemed to me equally hopeless. If she had no love for
him then, no doubt, ambition would seal her lips: she would
remember the throne of Kamt, the glorious double crown, the
homage of the people, and in the pomp and glitter forget the awful
doom which alone could drive the usurping stranger from her path.
But if she loved him, then what…? then the great and subtle puzzle
of the eternally feminine, the mysterious workings of a woman’s
heart, of a woman who, in spite of the high culture, the civilisation,
the artistic refinement of this land, was pre-eminently exotic,
passionate, semi-barbarous in her love and her hate. Nay! I knew
not. How could I guess how she would act? Can man read the uncut
pages of that romance of which a woman only shows him the title
leaf?
But, in the meanwhile, the dangers round my friend seemed to
close in tightly. Ur-tasen with subtle cunning had worked upon the
loves, the jealousies of the two women who alone could save him,
while I was still a caged prisoner, and the hours were swiftly
speeding on.
Neit-akrit had disappeared, and Ur-tasen alone remained, quietly
standing before the altar of the goddess, with arms outstretched,
murmuring one of his pagan prayers, but as I still continued my
weary watch, it seemed to me that newly awakened though still
hidden life began to pervade the great and mystic temple. Within the
main aisle the hanging lamps were lighted one after the other by—to
me—unseen hands, and in the distance fresh young voices were
rehearsing a bridal chant. Behind me in the outer precincts I could
hear the muffled sounds of shuffling footsteps passing swiftly to and
fro, and although from where I was I could see nothing save the
brilliantly lighted and lonely sanctuary, yet I felt that around me
there was bustle and animation: the preparations for the coming
festivity.
I was carefully maturing my plans. Determined to keep well within
the shadow of my prison, I would wait quietly for the best moment
in which to attract Hugh’s attention. I was in no sense of the word
nervous or agitated; I even began to feel strangely drowsy and had
much difficulty in accomplishing my numerous yawns noiselessly.
The atmosphere became insufferably hot and heavy; clouds of
smoke from the incense and burning herbs were continually wafted
in through the window of my prison, and this no doubt was
beginning to make me stupid and sleepy.
Not knowing how time was going on, I had squatted into the
angle of the wall, with my knees drawn up to my chin, in an
irresistible desire for sleep.
Suddenly I heard heavy footsteps outside, slow and halting; trying
to shake off my drowsiness, I raised my head and listened. Through
the marble tracery of the gateway I could see the vague forms of a
group of men, who seemed to be carrying something heavy between
them. A great cloud of some peculiarly scented burning herb came in
a great wave right through the window and seemed literally to strike
me in the face, blinding me and making me gasp for breath.
Drowsiness became intolerable, and yet when I sleepily reopened
my eyes I saw the gigantic marble gateway slowly moving on its
hinges.… This sight roused me from my lethargy for the moment.…
My senses fully alive, I watched and waited.… It was pitch dark in
the farther end of my cell, but I heard the footsteps within three feet
of me, still shuffling and halting.… Through the open gateway the
shadows appeared less dense: noiselessly on my hands and knees,
keeping my shoulder close to the wall, I crawled towards the
opening.
The men had put their heavy burden on the floor: they did not
speak, hardly did I hear them breathing. My fear was lest they
should detect me before I had reached the gate, but they seemed
not to have noticed me, and now, one by one, they turned and filed
out. I was close to the opening, leaning against the wall, ready to
crawl out in the last man’s wake.… From the inside of my prison the
same unknown scent of some highly aromatic herb was wafted in
great clouds towards my nostrils… the fumes were overpowering,
and I was tired and sleepy from my long, anxious wait.… The men
had all slipped noiselessly through the opening… the cloak of the last
one had caught in a projecting bit of carving… he stooped quietly to
disentangle it… I could see his outline very clearly against the
lighted corridor beyond.… My lids fell heavily over my eyes… I tried
to shake off my torpor, for the last effort for freedom… but I was too
sleepy.… I could not move. A great whiff of that enervating, burning
herb made me long for rest and sleep!… I was too tired… I would
slip out by-and-by.… Now I must have sleep.
The man with the cloak had slipped out… I think the gate swung
to, and I crouched once more with my chin between my knees.… I
wondered what the herb was.… I must find out… it would do instead
of ether in cases of minor operations… it was sweet and pleasant,
but overpowering.
From the sanctuary a sudden brilliant ray of light struck for an
instant through the aperture… some one must have gone past
carrying a lamp or torch. It lit up the centre of my prison, and forced
me to open my eyes for a second.… During that second I saw that,
on the floor, sharing my captivity with me, was the body of the
murdered Pharaoh.…
Then I remember nothing more.…
CHAPTER XXVI.
THE MARRIAGE
“And thou, oh, stranger, who dost hail from the foot of the throne of
Osiris, who art the son of Ra, the emissary of Horus, the beloved of
all the gods, tell Isis, the mysterious goddess, why thou art here.”
“I am here to crave of Isis the pure, Isis the beloved, Isis the most
holy, that she deign to pour the fruits of her blessing upon me, for I
would take this woman to be my wife.”
It was Hugh’s voice which spoke slowly and solemnly, and which
was the first sound that penetrated to my brain, still wandering in
the realms of cloud-land.
Through the window of my prison an intense flood of light filtered
brilliantly, illuminating the granite floor and walls. A strong scent of
incense and myrrh had driven away the stupefying fumes of that
burning herb which had lulled me to sleep. I tried to collect my
scattered senses, but a terrible pain in my head and eyes still kept
me half-stupefied. And yet I heard Hugh’s voice speaking strange
and momentous words, and a dull instinct whispered to me that I
must get to him, somehow, for a reason, of which I was not as yet
fully conscious. A raging thirst had made my tongue swell and
parched my throat: the events of the last few hours danced before
my clouded brain like some weird phantasmagoria.
The Pharaoh… dead! murdered! his body lying close to me, when
last I had opened my eyes, but now, carried away, while I had been
asleep… Maat-kha!… the murderess!… Hugh’s promised bride! Ur-
tasen, the evil plotter!… who had done… I knew not what…
something that would wreck Hugh’s life as well as his honour.… Neit-
akrit!… who might be a friend, and yet was a foe!… and I… a
helpless prisoner, stupid, senseless, half-drowsy still, after a drugged
and heavy sleep!
“And thou, Maat-kha, who art daughter of Uah-ab-ra, the son of
Ach-mes, the son of Ne-ku, tell Isis, the mysterious goddess, why
thou art here.”
I did not know that voice, some priest probably… no concern of
mine… I could perhaps get another half-hour’s sleep… I was still so
tired.
“I came here to crave of Isis the pure, Isis the beloved, Isis the
most holy, that she deign to pour upon me the fruits of her blessing,
for I would swear fealty to this man, and be his wife.”
That was Queen Maat-kha’s voice, and just now I had heard that
of Hugh… the pain in my head was intolerable… my limbs felt weak
and stiff: there was the whole length of my prison between me and
the aperture, through which probably I should be able to see those
who had spoken. I began to drag myself along, but I was only half
awake, my limbs only just managed to bear me along, and I did not
know if I should ever reach that aperture.
“Art awake, oh, Isis, who art daughter of Ra?
“Art awake, oh, Isis, who art sister and bride of Osiris?
“Art awake, oh, Isis, who art mother of Horus?
“Oh, Isis, give life to this man and to this woman, who have
sought the sanctity of thy temple!
“The gods above do rejoice! the glorious company is full of joy,
giving praise to thee, oh, Isis, who art pure!
“Isis who art beloved!
“Isis who art most holy!”
I had at last, after terrible difficulties, succeeded in reaching the
window; with infinite pain I struggled to my feet, but I could not
stand: my head was heavy and my knees shook under me. Twice I
fell down, but at the third struggle my hands convulsively fastened
on the marble ledge, and steadying myself as best I could, I looked
out, dazed, before me.
The sanctuary and the temple beyond it were one dazzling mass
of lighted lamps and torches. The gossamer curtain had been drawn
aside, and I could see the interminable vista of snow-white columns,
on which the silver inlay glistened with a thousand sparks. Between
the pillars, a sea of dark heads, adorned with gaily-coloured caps
and kerchiefs, amongst which, occasionally, I caught sight of the
glitter of a golden uræus, or elaborately jewelled belt.… I could
distinguish no details: my eyes were blurred, my brain overclouded.
I remember that gorgeous picture only as one remembers a dream.
Immediately before me Isis towered, wrapped in her sacred
mantle, which hand of man has never dared to touch. On her head a
gigantic pair of snow-white horns, between which glittered the silver
disc of a huge full moon. Immediately at her feet a group of priests,
with shaven crowns and long flowing robes of white, stood in a
semi-circle, in the middle of which the high-priest of the goddess
stood with arms outstretched, reciting the invocations.
Beneath the many hanging lamps, wherein burned lights of
different colours, the other priests of the gods of Kamt were massed
in imposing groups: the priests of Ra with yellow robes and leopard
skins round their bodies: those of Phtah, with monstrous scarabæus
of iridescent blue and green enamel on the top of their heads: those
of Thot, with masks of apes entirely covering their faces, and those
of Hor, with masks of sparrow-hawks, while the jackal’s head hid the
features of the priests of Anubis. Immediately to the right of the
officiating high priests stood Ur-tasen, the high priest of Ra.
“Isis is strong!
“Isis is great!
“Isis is living and mighty!”
The various attributes of the goddess reached my dull ears only as
the sound of muffled drums.
At the foot of the sanctuary steps, against a background of men
and women in gorgeous raiments, and beneath a canopy of white
lilies, stood Hugh Tankerville and his promised wife. His face was
even paler than when I had seen it last: his eyes gleamed darkly and
with an unnatural fire. He held his arms tightly crossed over his
chest, and in his whole attitude there was the expression of an
indomitable will triumphing over an overwhelming passion.
I saw him, as I had seen the sanctuary, the goddess, the crowds
of people, only as one sees a vivid dream. It seemed to me as if he
were not really there, but that slowly, very slowly, I was waking from
that sleep which had held me enthralled for months, and that when I
was fully awake I should look round me, and see myself sitting in
the dear old Museum, at The Chestnuts, with Mr. Tankerville sitting
beside me, telling me of beautiful, mysterious, legendary Neit-akrit.
I tried to speak to Hugh, for he was not far from me, but my
tongue seemed rooted to my palate, and, as in a dream, not a
sound escaped my throat. Clouds of incense rose all around, and
when the high priest had ceased to laud the magnificence of his
goddess, the priestesses, clad all in white, with their huge,
disfiguring wigs over their heads, began a sweet and monotonous
chant, accompanying themselves upon their crescent-shaped harps,
and beating upon the sistrum and the drum.
Beside Hugh, underneath that same canopy of lilies, and with her
hand holding his, was Queen Maat-kha. She had discarded her
gorgeous funereal draperies, and was standing clad all in white, her
regal crown over her low, square brow, her great black tresses
descending each side of her pale face, almost to her knees, and
intertwined with ropes of pearls. And I, in my dream, thought that I
could see, clinging to her finger tips, the last drops of her murdered
son’s blood.
Again I tried to scream, but my throat seemed paralysed.
Gradually memory, as a vague, still indistinct shadow, began to
creep back into my mind. Hugh was before me clad in sumptuous
robes, his dark head uncovered, his tall figure erect, ready to plight
his troth, to pledge that word, which he worshipped as a divinity, to
the vile murderess by his side. Twice a murderess, since having slain
her son she would ruthlessly sacrifice her lover to save herself from
the tortures of jealousy. Yes, I did remember! It was imperative that
I should warn Hugh of some terrible danger which the woman
beside him and the high priest of Ra had placed across his path.
“Oh, thou who art beloved of the gods, and thou who art Queen
of Kamt, behold! Isis the goddess is awakened!
“Ra, all-creating, all-powerful and mighty, doth descend to earth!
“Phtah, the mysterious, and Osiris, the bounty-giver, do hover
invisibly over your heads!
“But Hapi, who proceedeth from Ra, who, in his divine person, is
the living representative of Isis, of Osiris, and of Phtah, Hapi himself
will pass before your eyes!

PDF The Organotransition Metal Chemistry of Poly Pyrazolyl Borates Part 1 First Edition Fink Download

Uploaded by

Copyright:

Available Formats

PDF The Organotransition Metal Chemistry of Poly Pyrazolyl Borates Part 1 First Edition Fink Download

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

PDF The Organotransition Metal Chemistry of Poly Pyrazolyl Borates Part 1 First Edition Fink Download

Uploaded by

Copyright:

Available Formats

Full download ebook at ebookname.

The organotransition metal chemistry of poly

Download more ebook from https://ebookname.com

The Survey Kit 2nd edition The Survey Handbook 1 Dr.

The Greek State at War Part 1 The Greek State at War

Role of Poly Vinyl Chloride in Healthcare 1st Edition

Bakemonogatari Part 1 Monster Tale Nisioisin

Design of Plated Structures Eurocode 3 Design of Steel

The Craft of Musical Composition Book 1 Theoretical

The Chemistry of Cyclobutanes in 2 part 1st Edition Zvi

The Chemistry of Heterocyclic Compounds Oxazoles

First edition 2015

© 2015 Elsevier Inc. All rights reserved

For information on all Academic Press publications

Joseph A.B. Abdalla

Coordination and Activation of

Advances in Organometallic Chemistry, Volume 63 # 2015 Elsevier Inc. 1

pin pinacolato, OCMe2CMe2O

Mes Mes Mes Mes Mes Mes Dipp Dipp

IMes 5-Mes 6-Mes 6-Dipp

Donation from filled Back-bonding into EJH

More ⬙side-on⬙ alignment allows

κ1 or κ2 binding—that is featuring interactions with the metal center

2. BORANE (BdH) σ-COMPLEXES

anion. Of key importance in rationalizing the bonding in complexes con-

2.1 σ-Complexes Featuring Tetra-Coordinate Boranes

exchange of bridging and terminal BdH bonds typically results in a statis-

significantly lower than those found, for example, in the corresponding

PiPr3 PiPr3 NMe3

Scheme 4 Syntheses of group 9 metal complexes featuring κ2 amine borane ligands.29a,b

electronic and geometric structure, systems featuring NdH bonds are

dehydrogenation reaction occurring between the H3BNMeH2 monomer

2.2 σ-Complexes Featuring Tri-Coordinate Boranes

significant activation of the BdH bond. The solid-state structure of 25

corresponding chloroborane (Scheme 7). This route proves to be particularly

R2 = cat 28, pin 29, Cy2 30

Me5 Me5 Me5

With much interest being focussed on the catalytic dehydrogenation of

impact of the metal fragment on the electronic/geometric structures of

Related to systems 44–46 are cationic group 9 complexes formed by

metal center, leading to dehydrogenation and the formation of a subvalent

PCy3 PCy3 vacuum PCy3

complex—dehydrogenation generates [(p-cym)Ru(PCy3)(H)(]BNiPr2)]

(in this case brought about by abstraction of a chloride coligand) can be

3. ALANE (AldH) σ-COMPLEXES

111.3° and that in Cp0 Mn(CO)2(HBcat) is 89.1°.26,32 Presumably, differ-

tricarbonyl systems in an attempt to enforce κ3-alane coordination, result

(M ¼ Cr, Mo, W) fragments have been synthesized and structurally

ArCl Dipp ArCl

Dipp OCCo(CO)3 Dipp OCCo(CO)

[(OC)3Co(μ-H)2Al{(NDippCMe)2CH}][Co(CO)4], 79 (Fig. 11). This sys-

4. GALLANE (GadH) σ-COMPLEXES

Me3NAlH3 is stable at room temperature and can be sublimed at ca. 40 °C,

analogous borane complexes, an assertion backed up by preliminary data

donor/acceptor complexes featuring the Ga(I) carbenoid ligand {HC

M(CO)5[Ga{(NDippCMe)2CH}] (and H2), with the additional carbonyl

Fe(CO)4Ga{(NDippCMe)2CH} (90).18 In the case of Mn2(CO)10, how-

formed (E ¼ B, Al, Ga), with the greater propensity of boron to undergo

(M ¼ molybdenum or tungsten; R ¼ Cy or isopropyl). Evidence for a side-on bonded