Beyond Conventional N-Heterocyclic Carbenes: Abnormal, Remote, and Other Classes of NHC Ligands With Reduced Heteroatom Stabilization

Chem. Rev.
2009, 109, 3445–3478 3445
Beyond Conventional N-Heterocyclic Carbenes: Abnormal, Remote, and Other

Classes of NHC Ligands with Reduced Heteroatom Stabilization
Oliver Schuster,*,† Liangru Yang,‡ Helgard G. Raubenheimer,† and Martin Albrecht*,‡
Department of Chemistry, University of Stellenbosch, Private Bag X1, 7602 Matieland, Stellenbosch, South Africa, and Department of Chemistry,
University of Fribourg, Ch. du Musée 9, CH-1700 Fribourg, Switzerland
Received November 5, 2008
Contents 5.2. Hydrogenation and Hydrosilylation Reactions 3473

5.3. Olefin Metathesis 3475
1. Introduction 3445 6. Conclusions 3475
2. Methods of Ligand Complexation 3448 7. Acknowledgments 3476
2.1. Complexes with C4-Bound Imidazolylidenes 3448 8. Note Added after ASAP Publication 3476
2.1.1. C-H Bond Activation of Unsubstituted 3448 9. References 3476
2H-Imidazolium Salts
2.1.2. C-H Bond Activation of C2-Substituted 3449
Imidazolium Salts 1. Introduction
2.1.3. Coordination to Free Carbenes 3453 The organometallic chemistry of N-heterocyclic carbenes
2.1.4. Oxidative Addition 3454 (NHCs) has experienced explosive development during the
2.2. Triazolylidene Complexes 3454 last few years, and the topic remains the main focus of many
2.3. Pyrazolylidene and Isothiazolylidene 3454 outstanding research programs.1 The ongoing popularity of
Complexes this research area is certainly due to the development of
2.3.1. C-H Bond Activation 3454 extremely active catalyst systems comprising such carbene
2.3.2. Transmetallation 3455 ligands. This is perhaps most clearly illustrated by the
second-generation olefin metathesis catalysts developed by
2.3.3. Oxidative Addition 3455
Grubbs and Nolan,2 or by the cross-coupling catalysts
2.3.4. Nitrogen Functionalization of Metallated 3456 introduced by Organ and currently commercialized by
Pyrazolyl Ligands
Aldrich.3
2.3.5. Cycloaddition to Fischer Carbene 3457
Complexes The potential of NHCs as ligands for transition metals has
2.4. Pyridylidene Complexes 3457 been pioneered, in particular, by the independent work of
Öfele and Wanzlick, and, later, also by Lappert and Stone
2.4.1. Oxidative Addition 3457
in the 1960s and early 1970s.4 Despite the considerable
2.4.2. Nitrogen Functionalization of Metallated 3459
Pyridyl Ligands progress achieved by these groups, the topic did not attract
widespread attention until Arduengo reported on the isolation
2.4.3. C-H Bond Activation 3461
and stability of free N-heterocyclic carbenes.5 This discovery
2.4.4. P-C Bond Activation 3465 marked a watershed in carbene complex chemistry, and these
2.4.5. Cycloaddition to Fischer Carbene 3465 ligands became available from convenient and inexpensive
Complexes precursors such as imidazolium salts. A key factor in the
2.5. Complexes Comprising Cyclic (Amino)(Alkyl) 3466 remarkable stability of Arduengo-type free carbenes lies in
or (Amino)(Ylide)Carbenes the almost-excessive heteroatom stabilization, because of the
2.5.1. Coordination to Free Cyclic 3466 presence of two heteroatoms, at least one of which is
(Amino)(Alkyl)Carbenes typically a nitrogen in a position R to the carbene carbon (A
2.5.2. Oxidative Addition 3466 in Figure 1).5 The chemistrysand, specifically, the coordina-
2.5.3. C-H Bond Activation 3466 tion behaviorsof these “classical” heterocyclic carbenes has
2.5.4. Cycloaddition to Fischer Carbene 3467 been reviewed extensively: monographs as well as special
Complexes issues have dwelled on this topic.1
2.5.5. (Amino)(Ylide)Carbenes 3468 Rather dormant in the beginning of the new millennium,
2.6. Miscellaneous N-Heterocyclic Carbenes with 3469 the concept of heterocyclic carbene ligands that are not
Low Heteroatom Stabilization stabilized by two adjacent heteroatoms, as in Arduengo-type
3. Carbenes or Zwitterionic Ligands? 3469 carbenes, and also not necessarily with heteroatoms placed
4. Donor Properties of the Ligands 3471 in a position R to the carbene carbon was revived by a
5. Catalytic Applications 3471 serendipitous discovery of C4 bonding in imidazolylidenes.6
5.1. Carbon-Carbon Cross-Coupling Reactions 3471 The large class of heterocyclic carbenes that can be grouped
together under the title of this review include, in particular,
* Author to whom correspondence should be addressed. Phone: +41-26- imidazolium-derived ligands that bind the metal via the C4
3008786. Fax: +41-26-3009738. E-mail: [email protected], or C5 carbon (B and C in Figure 1) as well as the
[email protected].
†
University of Stellenbosch. pyridylidene family with only one heteroatom present in the
‡
University of Fribourg. heterocyclic skeleton (D-F in Figure 1). Variations on this
10.1021/cr8005087 CCC: $71.50  2009 American Chemical Society
Published on Web 03/30/2009
3446 Chemical Reviews, 2009, Vol. 109, No. 8 Schuster et al.
Oliver Schuster studied chemistry at the Technical University of Munich Helgard G. Raubenheimer was born in South Africa. He studied at the
(Germany) and obtained his Ph.D. there in 2005, under the supervision University of Stellenbosch near Cape Town, and, after 28 years as senior
of Prof. Hubert Schmidbaur. For postdoctoral studies, he moved as a lecturer, professor, and HOD at the University of Johannesburg (then
Feodor Lynen Fellow (Alexander von Humboldt Foundation) to Prof. RAU), he returned in 1998 to Stellenbosch as Head of Department
Helgard Raubenheimer’s group (University of Stellenbosch) in South Africa, (Chemistry and Polymer Science) and Professor in Inorganic Chemistry.
where he investigated the concept of remote N-heterocyclic carbenes. His main research interests are the chemistry of gold and reactivity of
Oliver is currently a Leopoldina Postdoctoral Fellow (German Academy complexes with carbene ligands. A long time ago, he worked for two
of Sciences) in the laboratory of Prof. Martin Albrecht at the University of years with E.O. Fischer in Munich and with Dieter Seebach in Zurich.
Fribourg in Switzerland. His current efforts are dedicated toward the Recent collaborators include Hubert Schmidbaur, Wolfgang Herrmann,
establishment of new routes to 4-pyridylidene metal complexes to and Gernot Frenking.
overcome limitations in their synthesis.
Martin Albrecht studied chemistry at the University of Bern (Switzerland)

Liangru Yang is a native of People’s Republic of China. She obtained and received his Ph.D. under the supervison of Prof. Gerard van Koten
her B.Sc. in Chemistry in 1998 and Ph.D. in 2003 at Zhengzhou University, from Utrecht University (The Netherlands) in 2000. After postdoctoral
working with Academician Yangjie Wu on ferrocene chemistry. After studies with Robert H. Crabtree (Yale) and with Ciba SC (Basel,
postdoctoral research at Innsbruck University with Prof. M. R. Buchmeiser, Switzerland), he joined the University of Fribourg as an Alfred Werner
at University of Fribourg with Prof. A. von Zelewsky and Prof. M. Albrecht, Assistant Professor. His research program currently revolves around
and EPFL with Dr. O. Mamula, she joined He’nan University of Technology (bio)organometallic themes, with a special emphasis on developing new
in 2007. Her current research interests focus on the development of carbene ligands for catalytic and electronic applications. He has recently
transition-metal-catalyzed reactions and their application in organic been awarded a prestigious ERC Starting Grant from the European
synthesis. Research Council.
theme are found via the replacement or displacement of one

N atom, thus providing carbenes derived from pyrazolium, the synthetic routes that have been established for the
isothiazolium, and even quinolinium salts that contain a preparation of such complexes, covering the literature from
stabilizing heteroatom in a remote position (G-J in Figure the very beginning of activities in this area up to 2008. While
1). Recently, carbenes such as K, which are comprised of specialized reviews on some aspects of the present topic have
only one heteroatom and lack delocalization through the recently appeared,7 a comprehensive overview of the subject
heterocycle, have been discovered as versatile ligands, thus has not been available thus far. Rather than just being
constituting another important class of carbenes with low descriptive, the present account is mainly directed toward
heteroatom stabilization. Both the synthesis of the organo-
the impact of these still unusual metal-carbene bonding
metallic complexes of these ligands as well as the (catalytic)
properties of the coordinated metal centers generally show modes on the electronic properties and on the new catalytic
distinct differences, compared to the more classical NHC applications that have been realized by employing such new
complexes, such as C2-metallated imidazolylidenes. This carbene complexes. As a consequence of our focus on
review intends to describe such differences and highlights complexes with less-stabilized heterocyclic ligands, systems
the chemical peculiarities of these types of N-heterocyclic comprising acyclic carbenes have not been included, and the
carbene complexes. It introduces, in a qualitative manner, interested reader is, instead, referred to the pioneering and
Chemical Reviews, 2009, Vol. 109, No. 8 3447
Table 1. Available Methods for NHC Metallation
metallation method ligand system
via free carbene • 2-imidazolylidenes and related ligandsa
• 4-imidazolylidenes (via 2-imidazolylidene rearrangement)
• cyclic (amino)(alkyl)carbenes (CAACs)
and (amino)(ylide)carbenes (AYCs)
C-H bond activation • 2-imidazolylidenes and related ligandsa

• 4-imidazolylidenes
• 4-triazolylidenes
• 3-pyrazolylidenes
• 2-, 3-, 4-pyridylidenes
• CAACs and AYCs
C-E bond activation • 2-imidazolylidenes (E ) CH3: activation with AgI; E ) CO2-:

activation with d8 metals; CdC activation of enetetramines)
• 2-pyridylidenes (E ) PR2: activation with PdII)
C-X oxidative addition • 2-imidazolylidenes and related ligandsa

• 3- and 4-pyrazolylidenes
• CAACs
transmetallation • 2-imidazolylidenes (predominantly from Ag complexes)

• 3-pyrazolylidenes (from Ag, Cr)
• 4-triazolylidenes
• 2-pyridylidenes (from Cr)
heteroatom alkylation • 3-pyrazolylidenes

cycloaddition to Fischer carbenes • 2-imidazolylidenes and related ligandsa

• 3-pyrazolylidene
• 2- and 4-pyridylidene
• expanded ring NHCs
a
Includes NHCs with two different stabilizing heteroatoms in a position R to the carbene.
A final preliminary remark concerns the controversial

classification of all these ligands as “carbenes”. While this
classification implies that the ligand is a neutral donor, in
all instances, a zwitterionic canonical representation consist-
ing of a carbanionic and a cationic iminium center may be
similarly appropriate and even necessary. When bonded, this
negative charge is obviously transferred to the metal in one
canonical form. Clearly, the borderline between the two
limiting representations is continuous, and the issue of
whether a ligand is, in reality, a carbene or not may become
Figure 1. N-heterocyclic carbenes, including the “classical” NHC semantic. In the case of the C2-bound imidazolylidenes,
representative (A) and representatives of subclasses comprising experimental and theoretical studies are in agreement with
reduced heteroatom stabilization (B-K); all are shown in their
carbene form. a relatively small π-contribution to the M-C bond only (M
) electron-rich metal center),12-14 and, hence, the M-C
ongoing work of Bertrand and co-workers.8,9 Similarly, interaction is typically represented by a single bond. How-
heteroatom-free cyclic carbenes are not further detailed ever, detailed studies involving less-stabilized N-heterocyclic
here.10 carbenes are still rare. Often, crystallographic and NMR
In the literature, different terms have been coined to spectroscopic arguments have been put forward to support
describe the bonding of such less-stabilized carbenes to metal one resonance form or the other. Despite the fact that the
fragments. For example, terms such as “wrong way”, metal-carbon bonds in Fischer carbenes and in N-hetero-
“abnormal”, “unusual”, or “nonclassical” have been used to cyclic carbenes are very much related, different means of
describe C4/C5-bound imidazolylidenes (B). Throughout this representation have evolved in the literature. In this review,
review, we refer to “abnormal” carbenes as those NHC single bonds are used to represent M-Ccarbene interactions,
ligands for which a canonical valence bond representation which is consistent with the accepted representations of
requires the introduction of additional formal charges on conventional NHC-metal bonds and even other metal-ligand
some nuclei (e.g., B, C, E, or I in Figure 1). The term bonds that are known to comprise significant π-character
“remote” carbene indicates that no heteroatom is located in (e.g., the M-CO bond in carbonyl complexes). Classical
a position R to the carbene carbon (e.g., E, F, H, I in Figure Fischer-type carbene complexes are written with an M)C
1); it may be possible to write uncharged contributing double bond, in agreement with a different convention
resonance structures for the free ligand.11 developed in the 1960s. A more complete discussion of these
multiple factors.18 Calculations suggest that C2 bonding and

C4 bonding proceed via distinctly different reaction pathways
involving either C2-H heterolytic bond cleavage or C4-H
oxidative addition, implicating an iridium(V) species (see
Scheme 2).19 Such mechanistic proposals were further
Figure 2. Metal complexes comprising normal (L) and abnormal supported by experimental data, which demonstrate that
(M) imidazolylidene ligands bound at the C2 and the C4 position,
respectively. product distributionsand, thus, the site of metallationsis
strongly anion-dependent. Large anions such as BF4- typi-
Scheme 1 cally are only weak partners for hydrogen bonding and effect
small changes in charge distribution. Consequently, such
anions favor an oxidative addition pathway, leading to
carbene C4 bonding. In contrast, smaller counterions such
as Br- accelerate heterolytic C-H bond cleavage through
hydrogen bonding, thus supporting a proton migration from
the imidazolium moiety to the metal-bound hydride. Ac-
cordingly, such anions preferentially yield C2-bound car-
benes. Time-dependent NMR analysis of the formation of 2
has revealed the intermediate formation of a hydrogenated
imidazolinylidene species 4.15 This result is consistent with
considerations is provided in Section 3, after synthetic an oxidative addition pathway that is comprised of an [IrH4]+
strategies have been introduced. The review concludes with species, which may reversibly transfer H2 from the metal
applications of such carbene complexes in catalysis. center to the imidazolylidene heterocycle. Notably, chelation
of the pyridine moiety is not essential and similar selectivities
2. Methods of Ligand Complexation in C-H bond activation have been observed with simple
imidazolium salts upon reaction with [IrH5(PPh3)2] in the
A variety of different methods have been established for
presence of pyridine.20
the complexation of less-heteroatom-stabilized NHC ligands.
Some of these methods are very similar to those yielding Recent studies by Esteruelas et al. on the metallation of
normal C2-bound imidazolylidene complexes, while others imidazolium salts such as 1 with the osmium hydride
are unique to a particular subclass of NHC ligands. The precursor [OsH6(PiPr3)2] have confirmed the relevance of the
different methods of NHC ligand complexation are compiled counteranion for the regioselectivity of metallation.21 Met-
in Table 1. Further details are provided in this section, which allation at the C4 position is again favored with large and
has been organized according to the different ligand systems unpolarized [BPh4]- anions, whereas imidazolium bromides
involved, rather than according to the methods used. afford, almost exclusively, the C2-metallated carbene. Time-
dependent analysis of carbene formation indicated that kinetic
2.1. Complexes with C4-Bound Imidazolylidenes factors are more relevant for C4 coordination than for C2
coordination. In addition, isomerization of the C4-bound
2.1.1. C-H Bond Activation of Unsubstituted carbene to its thermodynamically favored C2-bound isomer
2H-Imidazolium Salts has been accomplished under strongly acidic conditions in
the presence of HBF4.
Crabtree and co-workers15 were the first to observe
abnormal C4 metallation of imidazolium salts a few years The regioselectivity of metallation is further influenced
ago (Figure 2). The reaction of pyridine-functionalized by the wingtip substituents on the imidazolium salt.22 A
imidazolium salt 1 with the iridium polyhydride IrH5(PPh3)2 mesityl substituent promotes C4 bonding to the Os center 6,
also afforded the iridium (III) complex 2, which is comprised while the corresponding benzyl-substituted imidazole gives
of a carbene that is abnormally bound through C4 rather than the C2-bound carbene complex 7 in high yields (see Scheme
C2 (see Scheme 1). The coordination mode was deduced 3). The outcome of this reaction can be explained by
from NMR spectroscopy and was unambiguously confirmed invoking steric hindrance between the isopropyl groups of
by X-ray crystallographic analysis. No interconversion to the the phosphines and the imidazolium wingtip groups, which
presumably more-stable normal carbene complex 3 was is more pronounced for mesityl than for the comparatively
detected. Hence, product formation seems to be kinetically flexible benzyl substituent.
controlled. These results indicated, for the first time, that it A driving force different from counterion effects and
may not always be safe to assume C2 bonding when steric discrimination is required to rationalize the selective
preparing NHC complexes in situ from imidazolium salts C4 metallation of the imidazolium salt 8, which is
and a metal precursor. comprised of a chelating phosphine wingtip group to give
The activation of the C4-H bond in imidazolium salts complex 10 (see Scheme 4).23 With [Ir(cod)Cl]2 (where cod
such as 1 is remarkable when considering the acidity ) 1,5-cyclooctadiene), initial phosphine coordination and
difference between the two types of heterocyclic protons. formation of 9 has been observed. Subsequent C-H bond
The acidity of the proton attached to C2 has been determined activation occurs exclusively at the C4-position and is
experimentally and by calculation (pKa ) 24 ( 1).16 This reversible with ethylene-linked bidentate ligands, yet slow
value is 9 pKa units lower than that calculated for the C4- and irreversible with the analogous methylene-bridged
bound proton (pKa ) 33).17 The difference suggests that derivative 9a. Base-mediated reductive elimination affords
aspects other than the acidity of the protons control the the corresponding iridium(I) complexes 11. Furthermore,
regioselectivity of metallation. neither a small wingtip group nor a hard chloride counterion
The selective formation of C4- or C2-bound carbene (not shown) succeeds in promoting C2-H bond activation.
complexes with iridium hydrides seems to be dependent on Perhaps the affinity of iridium(I) for olefinic CdC bonds
Scheme 2
Scheme 3 addition, to give 13. The trans orientation of the two carbene
ligands seems to play a decisive role for C4 bonding. In
rigidly cis coordinating, chelating bis(carbene) complexes,
exclusive C2 bonding is observed under identical base-free
metallation conditions.25,26
2.1.2. C-H Bond Activation of C2-Substituted

Imidazolium Salts
Although the previous section illustrates the feasibility of
C4 bonding with 2H-imidazolium salts, which may be
particularly relevant for in situ complex formation, unpro-
tected imidazolium salts are primarily metallated at the C2-
position. A rational route toward C4-bound carbenes there-
fore includes the selective protection of the most acidic C2-
position, e.g., by incorporating alkyl or aryl substitutents.
might also play a role in the regioselectivity of iridation. In Thus, oxidative addition of the C4-H bond of the tetra-
addition, the constrained bulk of the coordinated phosphine alkylated C2-blocked imidazolium salt 14 to zerovalent
ligand could increase the steric sensitivity of the Ir Pt(norbornene)3, in the presence of equimolar amounts of
center. the free carbene IMes, yields the platinum hydride complex
Additives also have a distinct influence on the regiose- 15 with the mixed C2- and C5-bound carbenes both attached
lectivity of imidazolium palladation. Metallation of the to platinum (see Scheme 6).27 The formation of this complex
hydrochloride adduct of N,N′-dimesitylimidazol-2-ylidene has been proposed to occur stepwise. Initial coordination of
(IMes · HCl) with Pd(OAc)2, in the presence of Cs2CO3 as a the basic IMes provides the necessary electron density at
base, occurs selectively at the C2-position, thus affording the central metal to allow for subsequent oxidative addition
the normal bis(carbene) complex 12 (see Scheme 5).24 In of the imidazolium C4-H bond. A similar reaction sequence
the absence of Cs2CO3, however, the heteroleptic complex may apply to the formation of the abnormal/normal
13 is formed. It is comprised of one C2-bound NHC ligand [Pd(IMes)2Cl2] complex 13 (Vide supra). When using the
and one carbene that is bound abnormally at C4 to the asymmetrically 1,2,3-trialkylated imidazolium precursor 16,
palladium center (see Scheme 5). Interestingly, an X-ray a mixture of C4- and C5-bound isomers 17a and 17b is
structure analysis shows that the two different Pd-C bond formed in a 3:1 ratio. This product distribution might reflect
lengths are identical within experimental error (Pd-C ) a moderate steric preference in the transition state of the
2.019(13) and 2.021(11) Å for the normal and abnormal oxidative addition.
carbene, respectively). According to the mechanistic model Complexes 17 are unstable in the presence of certain
used for iridium metallation (Vide supra), the CO32- anion alkenes, such as styrene, and undergo reductive elimination.
may promote heterolysis of the most acidic C-H bond, thus The C4-bound carbene is significantly more prone to
favoring formation of C2-bound complexes. In the absence reductive elimination than the C2-bound IMes ligand, leading
of a base, the C4-H bond is activated, probably by oxidative to the exclusive formation of the imidazolium salt 16 and
Scheme 4
Scheme 5
Scheme 6 a Tolman electronic parameter (TEP)29 of ν ) 2039 cm-1

has been estimated. This value is considerably lower than
for analogous C2-bound carbenes (ν ≈ 2050 cm-1) or basic
phosphines (cf. PCy3, ν ) 2056 cm-1). Hence, such C4-
bound carbenes are among the best neutral donors known.
Complex 19a has been demonstrated to be a useful metal
precursor for transmetallation. In the presence of a Ag-
triazolylidene, swift formation of the normal/abnormal bis-
(carbene) complex 20 is observed.30 Complexes such as 20
generally exist as multiple diastereoisomers, since rotation
about the Ir-Ccarbene bonds is hampered by the two cis-
coordinated carbene ligands. Initial attempts to separate the
diastereoisomers of 20 by recrystallization have been unsuc-
cessful; yet, this may become an attractive methodology for
application in asymmetric catalysis.
Notably, the formation of stable abnormal silver carbene
the Pt0 complex, Pt(IMes)(diolefin). No products resulting complexes for transmetallation is often limited to imidazo-
from reductive elimination of the normal C2-bound carbene lium salts with aryl substituents at the C2-position, because
nor from alkene insertion into the Pt-H bond are observed. primary or secondary alkyl groups have been found to be
Both, electronic and steric reasons may account for the unreliable protecting groups.31 Reaction of Ag2O with
observed reaction outcome, and further investigations are 2-methylated or 2-benzylated imidazolium salts 21 initiates
clearly desirable. an unexpected C-C bond activation process, thus yielding
C4-bound carbene metal complexes can also be made by the normal Ag-carbene complex 22 (see Scheme 8). A
transmetallation from the corresponding silver complexes. detailed analysis of the course of reaction reveals that Ag2O
Precursor Ag-NHC complexes are typically generated from is gradually oxidizing the carbon that is attached to C2 to
silver oxide (Ag2O) and imidazolium salts.28 To achieve yield acyl imidazolium salts and metallic silver. In the
selective metallation, it is necessary to protect both the C2- presence of water that is formed during this redox reaction,
and C5-positions. For example, the disubstituted imidazolium acyl functionalities seem to be good leaving groups and,
salt 18 undergoes clean deprotonation in the presence of hence, promote metallation at the C2 carbon. Consistent with
Ag2O.20 Subsequent transmetallation of the presumably this mechanistic scheme, the highest yields are obtained when
formed silver complex with [Ir(cod)Cl]2 yields the Ir+ a large excess of silver salt is used. A similar oxidation is
complex 19a, and after the exchange of spectator ligands effectively suppressed when a quaternary carbon (e.g. a
(cod for CO) complex 19b (see Scheme 7). IR spectroscopy phenyl group) is attached to C2.
of this dicarbonyl complex allows for an estimation of the A transmetallation protocol has been applied for the
electron-donating ability of such C4-bound carbenes. From synthesis of a series of complexes 24 that are comprised of
the observed stretching frequencies (νCO ) 2045, 1961 cm-1), abnormally bound imidazolylidene-derived ligands (see
Scheme 7
Scheme 8
Scheme 9
Scheme 9).32 Remarkably, the donor properties of these Scheme 10

ligands, according to νCO IR analyses, seem to be tunable
by remote ligand modification, such as the incorporation of
functional groups R in the benzyl wingtip group or by
annealing another benzene unit to the carbene ligand 25. The
carbene ligand in complex 25 becomes a stronger σ donor
and a better π acceptor, because of the presence of the
annelated aromatic ring. However, remote ligand function-
alization may also affect the CO ligand by stereoelectronic
effects, which do not directly reflect the ligand donor
properties (cf. Section 4).
Despite the notorious instability of C4-bound carbene
silver complexes, successful transmetallations have recently
been reported from silver carbenes derived from 1,2,3- stronger donors than normal carbenes. Such a conclusion is
trimethylimidazolium salts, which are comprised of a hy- corroborated by a shift toward lower frequency in the infrared
drogen at the C5-position.33,34 While yields are generally low, stretching vibrations of related dicarbonyl Ir+ complexes, as
product formation at room temperature indicates that the previously mentioned. Moreover, the abnormal dicarbene
stability of the Ag complex may be sufficiently high to complexes 27 are very sensitive to acids and, in the presence
provide access to the desired product. of H2SO4, demetallation occurs within a few minutes. In
In contrast to the silver complexation with Ag2O, palla- contrast, the normal analogues 28 are stable under identical
dation of C2-alkylated imidazolium salts does not affect the conditions, even at elevated temperatures.36 The former
C-C bond. For example, metallation of the potentially reactivity has been suggested to reflect an increased nucleo-
bidentate carbene precursor 26 with Pd(OAc)2 affords the philicity of the palladium(II) center in 27, because of the
dicarbene complex 27 without any detectable amounts of stronger donor ability of the C4-bound carbene, compared
C2-bound products (see Scheme 10).35 This procedure is to the 2-imidazolylidenes. Theoretical studies by Frenking
virtually identical to the C2 metallation of 2H-imidazolium and co-workers support this conclusion.37 The difference in
salts and avoids the presence of any free base (cf. 28). donor ability has been rationalized predominantly by the
Mechanistically, the metallation probably proceeds via an higher energy of the σ lone-pair that belongs to the carbon
ion-pair association, which is initiated by iodide coordination in C4-bound carbenes. Interestingly, these calculations further
to the palladium precursor to form the nucleophilic palladate suggest a virtually equal relative π contribution to the overall
[PdI2(OAc)2]2-. M-Ccarbene bond from C2- and C4-bound carbenes.
Because of the availability of the corresponding normal Unequivocal evidence for a strong electronic impact of
(28) and abnormal (27) palladium dicarbene complexes,26 it the imidazolylidene bonding mode has been provided by
has been possible to compare the respective bonding effects studies on the sterically comparable dicarbene complexes 29
imposed by C2 and C4 on the metal. X-ray photoelectron and 30 with C2- and C4-bound dicarbene ligands, respec-
spectroscopy (XPS) indicates a 0.6 eV higher bonding energy tively (see Figure 3).38 Structural disparity between the two
for the palladium core electrons when coordinated to the complexes arises predominantly because of the different
normal carbenes. This difference in electron attraction again Pd-Cl bond lengths, as a consequence of the stronger trans
suggests that abnormally bound carbenes are considerably influence of the C4-bound carbene ligand. However, the
Scheme 13
Figure 3. Sterically identical palladium(II) complexes that are

comprised of differently bound dicarbene ligands.
Scheme 11 Scheme 14
ligand precursor 35.33 In the presence of NaOAc, smooth

formation of the chelate 36 was observed (see Scheme 13).
reactivity of the complexes varies considerably. Coordination No activation of the exocyclic C-H bond was evidenced,
to Ag+, acid lability, and easier reductive carbene elimination suggesting that the formation of complexes such as 33 might
occur in the C4-bound carbene complexes, while the C2- be a consequence of the initial carbene bonding to the iridium
bound complexes 29 are inert under identical conditions. center in the abnormal bonding mode.
These results indicate that the carbene ligand binding modes Lassaletta and co-workers synthesized NHC rhodium(I)
in the two complexes differ to such an extent that the complexes, which were comprised of a C4-bound carbene
complex reactivity, which is typically determined by the ligand (see Scheme 14).40 The base-containing metal precur-
molecular orbitals located on the metal, is substantially sor was prepared in situ by reacting [Rh(cod)Cl]2 with
influenced. K[N(SiMe3)2].41 Subsequent metallation of the pyridine-
Using a similar C-H bond activation protocol, related anellated imidazolium salt 37, featuring a phenyl-protected
rhodium(III) dicarbene complexes 31 were also prepared (see C2-position, thus yielded the C4-bound carbene rhodium(I)
Scheme 11).39 The metallation, using [Rh(cod)Cl]2, pro- complex 38. IR spectroscopic data of the corresponding
ceeded considerably better when the reaction was performed dicarbonyl complex 39 were very similar to those of related
in the presence of air and potassium iodide (KI) as well as iridium complexes with abnormal carbene ligands (e.g., 19b;
acetate. Detailed investigations revealed that the acetate acts recall Scheme 7), in agreement with a strong electron
as a proton scavanger rather than as a deprotonating agent. donation by the C4-bound carbene in 39.9,42 The iridium(I)
In addition, a sequential oxidation of iodide (by aerobic O2) complex analogous to 38 was prepared by transmetallation
and, subsequently, rhodium(I) (via the in situ formed I2) was from the corresponding Ag complex, a method which failed
proposed prior to Rh-C bond formation. The mechanism for rhodium.40
was further supported by the fact that, when starting directly A particular type of C4 metallation is shown in Scheme
from rhodium(III) precursors, diimidazolium metallation 15. Upon exposure of the C2-metallated yttrium(III) carbene
occurred in higher yields and with the formation of less side complex 40 to potassium naphthalenide, a rearrangement
products. occurs that furnishes a C4-bound yttrium(III) complex 41
With iridium(III) precursors, however, C-H bond activa- with a K+ ion now attached to C2.43 Formally, this process
tion at the C-bound CH3 group of the diimidazolium salt may be regarded as a carbene transfer from the yttrium center
26a was observed, thus yielding complex 33 (see Scheme to potassiumsa transmetallation process that is usually
12).33 This C(sp3)-H activation pathway is similar to that observed in the reverse direction. Complex 41 exists as a
observed with Ag2O (Vide supra). It was partially suppressed dimer and represents a rare example of a stable potassium
by extending the linker between the two imidazolium carbene complex that does not undergo demetallation via a
moieties from a methylene unit to an ethylene unit. This 1,2-alkyl shift. Notably, a second transmetallation with
modification provided the abnormal dicarbene complex 34b Me3SiCl ensues, again effecting a rearrangement of the
as the major product. These studies indicated that the direct yttrium fragment to the C2-position, and concomitant forma-
metallation must be used with caution, because selectivity tion of a new C4-Si bond in the product (complex 42).
is not always guaranteed. Clearly, such a two-step metallation has great potential, in
A related metallation procedure was applied for the particular when different (e.g., catalytically or redox active)
successful iridation of a mixed abnormal/normal dicarbene metal centers would be involved.
Scheme 12
Scheme 15
Scheme 16 C4 bonding mode, while the other one binds via two C2
carbene carbons. Again, the similar Fe-C bond distances
are independent of the bonding mode, and all fall within the
1.933-1.938 Å range.
Probably a related carbene rearrangement occurs after
deprotonation of the phosphine-functionalized imidazolium
precursor (47). Reaction of the presumed carbene in situ with
[Ir(cod)(µ-H)(µ-Cl)2]2 gave complex 48, which is comprised
of a C4-bound carbene (see Scheme 18).46 A similar complex
has been obtained from direct metallation of the imidazolium
salt via C-H bond activation (cf. 10; recall Scheme 4).
Conversely, coordination of a related free carbene ligand
to [Rh(coe)2(acac)] has exclusively yielded the C2-bound
2.1.3. Coordination to Free Carbenes phosphino-carbene complex.46 Metal-hydride formation
Normal C2-bound imidazolylidene metal complexes are could perhaps play an important role in the unexpected
often synthesized by a stepwise procedure that first includes carbene rearrangement when using iridium precursors.
the generation of a free carbene from the azolium salt with However, further studies are required to evaluate other
a strong base and subsequent metal coordination. Despite potential reaction pathways, such as proton migration from
the attractiveness of such a method, only a few reports have C4 to C2 during metallation. If the latter process indeed
appeared that describe abnormal NHC complex formation occurs, rearrangements may become more feasible than
that is preceded by free carbene formation. In most instances, expected.
C4 metallation has been an unexpected result and rational Notably, chelating groups are not required for such a
protocols are not available. Copper complexes that contain carbene rearrangement. A recent study on the reactivity of
nonclassical C4-bound carbene ligands have been isolated the cluster compound Ru3(CO)12 toward free carbenes
from the reaction of copper(I) salts with the tripodal carbene containing bulky wingtip groups has revealed the selective
ligand 43 (see Scheme 16).44 The resulting bimetallic formation of the abnormal carbene complexes 50 (see
complex 44 has each copper center bound to two C2-bound Scheme 19).47 The steric bulk imposed by the nitrogen
carbene units and one C4-bound carbene unit. This reaction substituents has been identified as a major driving force for
presumably involves tautomerization of the carbene site by this carbene rearrangement. When using imidazolylidenes
proton migration from C4 to C2. The NMR spectroscopic that contain smaller methyl wingtip groups, the major product
data reflect the different bonding modes (δC ) 189 for a C2 of the reaction is the trinuclear C2-bound imidazolylidene
carbene, δC ) 169 for a C4 carbene). In the solid state, cluster 49. Upon warming of the C4-bound carbene complex
however, the Cu-C bonds are all identical within the 3σ 50, a second irreversible C-H bond activation occurs, to
range (1.983 Å e Cu-C e 1.988 Å). afford the trimetallic complex 51 in which the heterocyclic
A similar rearrangement has been observed during the ring adopts a κ2-bridging mode.
reaction of the C,N,C pincer dicarbene ligand 45 with an A related, thermally induced carbene rearrangement was
Fe(II) complex (see Scheme 17).45 X-ray analysis of the observed in the Os cluster 52, which consisted of a normally
isolated complex 46b unambiguously revealed a heteroleptic bound IMes ligand (see Scheme 20).48 Upon thermolysis of
complex in which one pincer ligand displays a mixed C2/ 52 at 200 °C, the abnormal carbene complex 53 was
Scheme 17
Scheme 18 of the 1,4-disubstituted triazols 56 at the N3-position gives

compounds 57 as precursors for abnormal carbene bonding
(while N2-alkylation would provide normal carbene precur-
sors; see Scheme 22). Metallation of triazolium salts (57)
via C-H bond activation using Pd(OAc)2 or Ag2O, and
subsequent transmetallation of the silver carbene complex
with ruthenium(II), iridium(I), and rhodium(I) has been
Scheme 19 demonstrated. A preliminary assessment of the donor strength
of these 1,2,3-triazolylidene ligands has been accomplished,
based on the νCO stretching frequences of the iridium
dicarbonyl complex 59a. The resulting Tolman electronic
parameter29,53 compares well with those of the most basic
normal carbenes (cf. also 19b; recall Scheme 7). Adjustment
of the electronic effects of the heterocycle substituents has
been proposed as a method for fine-tuning the donor strength
of these ligands.
2.3. Pyrazolylidene and Isothiazolylidene

Complexes
Similar to imidazolium-derived carbenes, pyrazolium
metallation may give either normal or abnormal carbene
ligands. However, the heteroatom stabilization in pyra-
Scheme 20
zolylidenes is reduced, compared to that in imidazolylidenes.
In normal C3-bound carbenes, a single N atom is located
adjacent to the carbene carbon, which may increase the donor
properties of these ligands, compared to normal C2-imida-
zolylidenes. In abnormal C4-bound carbenes, only remotely
Scheme 21 located heteroatoms are available for carbene stabilization
(see Figure 4). Although the chemistry of abnormal pyra-
zolylidenes is somewhat underdeveloped, different routes to
normal C3-bound pyrazolyidenes have been disclosed. The
properties of the corresponding complexes reveal that this
type of ligand indeed is complementary in many respects to
its imidazolylidene counterpart.
obtained, along with various other products. Because of the
unusual reaction conditions, insufficient data are available 2.3.1. C-H Bond Activation
to make a sensible mechanistic proposal. Undoubtedly,
exciting further developments may be expected from the The pyrazolylidene complexes 64 were made via ther-
interaction of NHC ligands with transition-metal clusters.49 molysis of the pyrazolium salt of the decacarbonyl dimet-
allates 63 (see Scheme 23).54 Extended heating of the
2.1.4. Oxidative Addition molybdenum carbene 64a induced a ligand redistribution and
yielded the cis-bis(carbene) complexes 65 and Mo(CO)6.
As early as 1973, Stone and co-workers introduced the Although the corresponding 2-imidazolylidene complex that
oxidative addition of thiazolium salts to low-valence metal contains a N,N-dimethylimidazol-2-ylidene (IMe) ligand, cis-
fragments as a route to carbene complexes.50 This protocol (IMe)2Mo(CO)4, readily undergoes photochemical trans
is particularly attractive because metallation is entirely isomerization, complex 65 is inert toward such a rearrange-
independent of ligand CH acidity. Accordingly, the oxidative ment. This may be a consequence of the larger trans effect
addition of 4-haloimidazolium salts also represents a rational exhibited by the carbene ligand in 65. Based on carbonyl
access to C4-metallated carbenes. The potentially chelating stretching frequencies in Mo(CO)5 (carbene) complexes,
ligand precursors 54 were prepared by sequential regiose- Öfele and co-workers have attributed stronger donor proper-
lective H-substitution and N-alkylation of iodoimidazole. ties to the pyrazolylidene in 64 than to 2-imidazoylidenes
Oxidative addition to zerovalent Pd(dba)2 then afforded the such as IMe or benzimidazolylidenes. However, the trans
corresponding complexes 55 that carry abnormal carbenes influence is similar, i.e., the crystallographically determined
(see Scheme 21).51 metal-carbonyl bonds in the Cr complex 64b and (IM-
e)Cr(CO)5 are of equal length (Cr-COtrans ) 1.86 and 1.87
2.2. Triazolylidene Complexes Å, respectively).55
The formation of carbene ligands with reduced neighboring Quantum mechanical investigations suggest that the ni-
heteroatom stabilization has recently been demonstrated when trogen lone pairs of these heterocyclic carbenes are largely
1,2,3-triazolium salts were used as ligand precursors.52 The localized, thus allowing (some) mesomeric interaction solely
neutral triazol heterocycles are available by [3 + 2] cycload- via the carbon framework.55 This result is in marked contrast
dition reactions (“click chemistry”), which is a procedure to the general assumption that the stability of imidazol-2-
that is highly flexible and allows a variety of functionalities ylidene systems can be predominantly attributed to π-dona-
to be introduced in the ligand backbone. Nitrogen alkylation tion by the N atoms.1
Scheme 22
Scheme 23 Scheme 25
Scheme 24
Scheme 26
Table 2. Spectroscopic Data for Rhodium Complexes

Comprising Pyrazolylidene and 2-Imidazolylidene Ligands
compound νCO (cm-1) δC(carbene) 1
JRhC (Hz)
67b 2066, 1993 169.2 25.8
cis-(IMe)Rh(CO)2I 2073, 2000 168.9 40.8
cis-(SIMe)Rh(CO)2I 2072, 1999 195.2 n/a carbon correlate with the IR data, illustrating how uncertain
it could be to use such spectroscopic data to explain or
In an attempt to compare the relative donor strengths of deduce the bonding features of complexes.
different carbenes, Herrmann et al. have synthesized a range
of NHC complexes of the type cis-RhI(NHC)(CO)2.56 The 2.3.2. Transmetallation
complexes are prepared via in situ deprotonation of the Transmetallation methods are rather unexplored in pyra-
corresponding azolium salts by a metal complex that contains
zolylidene chemistry. Without isolation of the presumed
a basic ligand and the subsequent introduction of carbon
silver carbene complex, successful ruthenation afforded the
monoxide, as illustrated in the synthesis of complex 67b (see
complexes 69 and 70 (see Scheme 25).34 The stoichiometry
Scheme 24).41,57 The rhodium alkoxide precursor is effective
for the rhodation of various azolium salts; however, attempts of the reactants could be utilized to access either the
to use analogous alkoxide precursors of other metals have monocarbene 69 (0.5 mol equiv ruthenium dimer, with
been unsuccessful. respect to pyrazolium salt) or the bis(carbene) complex 70
The reported carbonyl IR stretching frequencies support (0.25 mol equiv).
the notion that the pyrazolylidene ligand exerts a higher
σ-donor/π-acceptor ratio than the unsaturated normal imi- 2.3.3. Oxidative Addition
dazolylidene IMe or its saturated analog (N,N-dimethylimi- The low CH acidity of pyrazolium salts has restricted their
dazolin-2-ylidene, SIMe; see Table 2). Neither 1JRhC coupling metallation by C-H bond activation to only few metal
constants nor the 13C NMR resonances of the metal-bound precursors thus far. Oxidative addition provides an alternative
approach (e.g., for the preparation of palladium complexes
72 from the 3-chloropyrazolium salt 71; see Scheme 26).57
At elevated temperatures, displacement of a phosphine ligand
by the nucleophilic Cl- anion is observed, yielding the neutral
Figure 4. Normal pyrazolylidene (N) bound via C3, and abnormal cis isomer 73. The metal-bound carbon appears at 162.7 ppm
(and remote) pyrazolylidene (O), coordinating to the metal center in the 13C NMR spectrum, which is only 1.6 ppm downfield
at C4. from 72.
Scheme 27 Scheme 32
Oxidative addition was also successfully used for the

synthesis of the first abnormally C4-bound pyrazolylidene Similar results were obtained using a cationic iron frag-
complex 75a (see Scheme 27).58 To increase the solubility ment (see Scheme 30).61 Carbene formation was assumed,
for 13C NMR analysis, iodide was substituted for trifluoro- based on a 19-ppm downfield shift of the metal-bound carbon
acetate to yield 75b. The carbene in the trifluoroacetate resonance upon remote protonation of the neutral precursor
complex 75b appeared at unusually high field (δC ) 113.8), 79. This assumption was further supported by a concomitant
thus representing one of the most shielded carbene-type bathochromic shift of the carbonyl absorption bands from
resonances known. This result could be a consequence of νCO ) 2031 and 1979 cm-1 in 79 to νCO ) 2048 and 1989
the combination of both abnormal and remote features in cm-1 in 80. However, neutral ligand formation alone could
this strongly electron-donating carbene. Further support for contribute to a decrease in metal-to-carbonyl back-donation.
strong ligand donation is provided by the low average νCO Single-crystal structure determinations revealed no significant
values (2018 cm-1) of analogous [Rh(CO)2Cl (carbene)] change in the Fe-C bond lengths upon carbene formation.
complexes, which are comprised of related C4-bound pyra- A similar procedure involving first transmetallation and
zolylidene ligands.58c subsequent N-alkylation has also been used to prepare the
isothiazolylidene complex 83 (see Scheme 31).62 A signifi-
cant downfield shift of the metal-bound carbon resonance
2.3.4. Nitrogen Functionalization of Metallated Pyrazolyl
(∆δ ) 25) occurs upon quaternization, and the carbonyl
Ligands
stretching frequencies again shifted to higher energies,
Another approach to preparing less-stabilized NHC com- presumably reflecting the formation of a metal-carbene
plexes involves first installing the metal on the heterocycle bond. Such a bonding mode is further supported by a
(R), followed by protonation or alkylation of the heteroatom relatively short C-S distance in the molecular structure of
to induce carbene-type bonding (S) (see Scheme 28). 83.
This approach has been successfully applied to the Related carbene formation has been also noted upon
preparation of a variety of carbene complexes with different alkylation of the anionic tungsten complex 84 to form 85
metals.59 Typically, metallation has been performed via (see Scheme 32).63 Remarkably, protonation instead of
lithiation of the azole-ligand precursor, followed by trans- alkylation does not yield the expected product. Instead, attack
metallation and protonation or alkylation. For example, at the metal-bound carbon provided, after a rearrangement,
transmetallation of the pyrazolyl lithium complex 76 with the N-coordinated isomer 86. Analysis of the 183W-13C
Cu(OTf) afforded the cuprate 77 and, after N-methylation, coupling constant of the isothiazolylidene complex 85 (δC
the bis(carbene) complex 78 (see Scheme 29).60 ) 197.8; 1JWC ) 75.0 Hz) indicates that the s character of
Scheme 28
Scheme 29
Scheme 30
Scheme 31
Scheme 33 Scheme 35
the overlapping orbitals at the carbene carbon is substantially

smaller in 85 than in the analogous C2-bound thiazolylidene
complex (δC ) 208.3; 1JWC ) 98.1 Hz). This fact might
explain the protonation at carbon to form the coordination
complex 86.
In contrast, alkylation of the imine N atoms in the
bis(isothiazolyl) aurate 87 have imparted only a small
downfield shift of the metal-bound carbon resonance (∆δ )
2.3).64 This concurs with little metal-to-ligand π-interaction
in complex 88 (see Scheme 33). Hence, an iminium rather
than a neutral carbene-type ligand resonance structure has
been postulated to make the more important contribution.
2.3.5. Cycloaddition to Fischer Carbene Complexes

Scheme 36
Cycloaddition of dinucleophiles to unsaturated Fischer-
type carbenes represents an alternative route to N-heterocyclic
carbenes.65 For example, the pyrazolylidene complex 90 has
been obtained upon addition of dimethylhydrazine to the
alkynyl carbene 89 or to the allenylidene 91 (see Scheme
34).
This synthetic route is particularly useful for the introduc-
tion of specific substitution variations into heterocyclic might be involved. Calculations have indicated that, in the
carbenes; yet, the yields for the cyclization step are typically absence of steric constraints, the ortho-pyridylidene (U) is
low. Recently, it has been shown that the pyrazolylidene in more stable than the corresponding meta-pyridylidene (V)
complex 90 is readily transferred to late transition metals. and para-pyridylidene (W) by 10-15 kcal/mol.69 Third,
This has been demonstrated by the synthesis of Au+, Au3+, chemical functionalization of pyridine is well-established,
and Pd2+ complexes (see Scheme 35), thus disclosing an which allows the carbene to be connected to a variety of
interesting cycloaddition-transmetallation sequence for pre- functionalities and be embedded in a variety of chelating
paring different pyrazolylidene metal complexes.66 environments. It is indeed surprising that the organometallic
chemistry of pyridinium-derived carbenes is still much less
2.4. Pyridylidene Complexes explored than the related imidazolylidene chemistry. This
may be the result of an intuitively wrong appraisal of the
Pyridinium salts represent a subclass of carbene precursors strength of such metal-carbene bonds.
that are remarkable in their own right. First, deprotonation
of a ring carbon formally produces six-membered N- 2.4.1. Oxidative Addition
heterocyclic carbenes that are stabilized by one heteroatom,
viz, the pyridylidene isomers U, V, and W (see Scheme 36). The first pyridylidene-type transition-metal complexes
The reactivity of such a putative carbene is high, and complex were prepared in 1974, via the oxidative addition of
formation according to a free carbene route is difficult. To pyridinium salts to low-valent metal centers. Reaction of the
date, free pyridylidenes, which were proposed by Hammick chloropyridinium salt 95 with iridium(-I) and rhodium(-I)
70 years ago,67 have been characterized only in the gas phase precursors gave the complexes 96a and 96b (see Scheme
by mass spectrometry.68,69 A recent computational study 37), respectively.71 Based on the pertinent CO stretching
suggests that free 2-pyridylidenes may be stable if the frequencies, the electron-donor capability of the N-methyl-
heterocycle is extensively substituted by electron-donating pyridylidene ligand was determined to be similar to that of
amino groups.70 Second, metal coordination at the ortho, other neutral ligands, such as PPh3 or DMSO. Upon reaction
meta, and para positions may provide normal, abnormal, and with methanolic LiCl, however, remarkably facile metal
remote carbene complexes. According to the definition of oxidation to the neutral Ir3+ complex 97 indicated an
the terms “abnormal” and “remote” (cf. Section 1), the appreciable electron density at the metal center in 96a.
abnormal 3-pyridylidene V belongs also to the class of A similar reaction was observed with the manganate
remote pyridylidenes. Similarly, the remote pyridylidene W Na[Mn(CO)5] as metal precursor.71 This method is also
is simultaneously a normal NHC. Regioselectivity is obvi- applicable to 4-chloropyridinium salts such as 99, thus
ously relevant, and electronic as well as steric influences affording the remote NHC complex 100 (see Scheme 38).72
Scheme 34
Scheme 37
Scheme 38 2-imidazolylidene complexes.77,78 Crystallographic analysis of

complexes 104-111 reveals metal-carbon bond lengths that
are in a range typically observed for M-Caryl single bonds.
These distances are also in good agreement with those of related
nickel(II) and palladium(II) imidazolylidene complexes. Based
on bond length analyses, the trans influence of pyridylidenes
increases with the distance between the heteroatom and the
carbene. This points to stronger donor properties of the remote
Upon metallation of 99, the 13C NMR resonance of C4 pyridylidenes.
experiences a significant downfield shift (δC ) 156 in 99 vs The electron redistribution within the N-heterocycle upon
226 in 100). This result, together with the increased νCO, formation of the complexes 104, 108, and 112 by successive
has been the basis for proposing carbene complex formation. methylation and metallation of 2-, 3-, and 4-chloropyridine,
Reaction of the chloropyridinium salt 95 with dianionic respectively, has been evaluated by means of 13C NMR
metalate complexes [M(CO)n]2- (M ) Cr, n ) 5; M ) Fe, spectroscopy.81 An additive contribution of the two inde-
Ru, n ) 4) yielded neutral complexes of the type [M(py- pendent steps can be deduced, which suggests that carbene
ridylidene)(CO)n], which is analogous to 100.71,73 Because formation is an incremental process. The degree of synergy
of the limited availability of dianionic precursors [MLn]2-, between both contributions is also reflected by the carbene
Schubert et al. explored the potential of monoanionic metal carbon NMR shift, which decreases in the corresponding
silyl and metal stannyl complexes [M(ER3)Ln]- (ER3 ) palladium complexes in the order
SiMe3, SnMe3) as synthons for [MLn]2-, because the ER3
ligand is readily removed in the form of R3ECl.74,75 The remote (δC ) 197.7) > normal (δC ) 189.3) >
feasibility of this approach was demonstrated by synthesizing abnormal (δC ) 165.0)
the pyridylidene complex 102 from the chloropyridinium salt
95 and the silyl-protected manganate precursor 101 (see Notably, the metal fragments exert a push/pull effect, which
Scheme 39). Spectroscopic properties of the pyridylidene is consistent with a carbene-type donor/acceptor bond. When
complex 102 are very similar to those of related Fischer compared to related chemical shifts in free pyridine, metal
carbene complexes (e.g., 103), which suggests a related complexation in the normal analogue 104 seems to affect
influence of the heteroatom on both metal-carbene bonds. only the immediate site of metallation, while a notable charge
A similar approach was used for the preparation of a rhodium redistribution within the heterocycle is induced in the remote
bis(pyridylidene) complex, which seems to be highly un- congener 108. A diene character of the normal and remote
stable.76 pyridylidene ligands is further supported by the bond
The oxidative addition of halopyridinium salts to several alternation observed in the X-ray crystal structures of 104
zerovalent precursors of Ni, Pd, and Pt allowed for systematic and 108. The data for the corresponding abnormal py-
study of the consequences of metallation at various positions ridylidene complexes 112 are more complex and cannot be
on the pyridinium ring.72,77-81 The metallation procedure has rationalized in terms of valence bond theory only.
a broad scope and was extended also to the metallation of Calculations using free reaction energies predict that
polyaromatic systems such as quinolinium and acridinium oxidative addition occurs more readily for 2-pyridylidenes
salts, thus providing access to abnormal and remote NHC than for 4-pyridylidenes, but, interestingly, the metal-carbon
complexes (see Figure 5).11 bond strength shows an opposite trend.78 Adjacent π-donor
The carbene carbons of the nickel and palladium complexes atoms may stabilize a free carbene toward nucleophilic attack
104-111 resonate at 200 ( 10 ppm and are significantly but simultaneously weaken the M-C bond. Similar results
deshielded (∆δC ) 40-50), compared to the corresponding have been obtained for Fischer-type carbene complexes.82
precursor pyridinium salts. The nickel-bound pyridylidene Metallation of the dichlorinated pyridinium salts 113 either
carbons are located at lower field strength than their palladium with Ni0 or with Pd0 exclusively provided the remote
analogues, which is opposite to the trend observed for the related pyridylidene product 114 (see Scheme 40).81 Taking into
Scheme 39
Figure 5. Pyridylidene nickel(II) and palladium(II) complexes, featuring different types of carbene bonding.
Scheme 40 Scheme 41
derived NHC complexes than in the corresponding 2-imi-

dazolylidene systems.77 Although the relative composition
account the absence of steric differentiation between the of the M-C bond seems to be remarkably insensitive to the
2-position and the 4-position in the protonated pyridinium position of the heteroatom, the calculated bond strengths vary
salt 113a, these results indicate that electronic considerations considerably.85 The total metal-ligand interaction energies
predominantly determine the regioselectivity of metallation. correlate well with the energy level of the HOMO in the
Thus, F-strain,83 which is induced by the substituents at free carbene ligand. Therefore, according to these compu-
nitrogen, may have a less-important role in directing the tational results, a less-stable free carbene yields a stronger
metallation to the 4-position than expected. metal-carbon bond.
Recently, the remote NHC concept has been extended to Cyclometallation of pyridinium derivatives via C-H bond
ligands in which the heteroatom and the carbene are located oxidative addition has been successfully utilized for the
in different aromatic rings.84 The Pd2+-bound carbon atoms synthesis of normal and remote pyridylidene iridium(III)
of 115 and 116 resonate at relatively high field (δC ) 180.7 complexes. To increase the regioselectivity for C2 metalla-
and 187.0, respectively; see Figure 6). Carbene bonding has tion, Li and co-workers have protected the potentially remote
been proposed based on the significant downfield shift of carbenoidal position by alkylation. Oxidative C-H bond
these signals, with respect to the corresponding ligand addition to [Ir(cod)2]PF6 gives the iridium(III) pyridine-
precursor salts. pyridylidene chelates (119 and 120) (see Figure 7).87 The
However, results of intramolecular competition experi- remote pyridylidene analog of 120 (viz., 121) undergoes
ments using the dichloride 117 have shown that oxidative cis-trans isomerization. The 121-cis complex has been
addition occurs exclusively at the heterocycle, yielding the crystallographically characterized and is also the major
remote pyridylidene-type complex 118. The C-Cl bond on species in solution. Such a regioselective C-H bond oxida-
the annelated ring is not affected at all, even in the presence tive addition protocol provides an attractive methodology for
of an excess of M(PPh3)4 (see Scheme 41).81 pyridylidene complex synthesis, because ligand prefunction-
Energy decomposition analysis of the M-C bond in alization becomes redundant.
various pyridylidene quinolylidene and isoquinolylidene
complexes have indicated that the attractive metal-ligand 2.4.2. Nitrogen Functionalization of Metallated Pyridyl
interactions are predominantly electrostatic, with only about Ligands
one-third due to orbital contributions.77,78,85 The covalent
portion consists of some 20% π-bonding, which compares In the early 1980s, the groups of Isobe88,89 and Crociani90-95
well with the π-character calculated for Fischer-type amino successfully prepared nickel, palladium, and platinum py-
carbene complexes.86 Both the σ- and π-contributions to the
M-C bond have been calculated to be larger in pyridinium-
Figure 6. Extension of the remote carbene theme: isoquinolylidene Figure 7. Normal pyridylidene Ir3+ complexes (119 and 120) and
complexes, which are comprised of the heterocycle and the metal- remote pyridylidene Ir3+ complexes (121), accessible by oxidative
bound carbene carbon associated with different rings. C-H bond addition.
Scheme 42 Scheme 44
Scheme 43
ridylidene complexes via the protonation or alkylation of Scheme 45

pyridyl complexes (see Scheme 42).
These early studies focused on the effect of the metal
fragment on the reactivity of the pyridine, rather than on
the carbene-type bonding of the ligand. Titration experiments
showed that the Brønsted basicity of pyridine in the pal-
ladium complex 123a is ∼4 orders of magnitude higher than
that of unsubstituted pyridine.89 Systematic studies revealed
a strong dependence of the basicity on the pyridyl substitution
pattern. The basicity decreases in the order of metal
substitution as C2 . C4 > C3, and it is larger for the
platinum complexes 125 than for the corresponding pal-
ladium complexes 123.89,95
Contribution of a carbene resonance structure in the
to the metal coordination plane, while in the pyridyl complex
protonated species 124a was inferred from 13C NMR
129, the ligand is tilted only by ∼10°.
spectroscopy. The resonance frequency of the metal-bound
The metal-carbon bond in 2-pyridylidene complexes such
carbene (δC ) 184.9) indicated a downfield shift, compared
as 124a displays a pronounced inertness. For example,
to the precursor pyridyl system 123a (∆δ ≈ 5). Moreover,
migratory insertion of isocyanide into the Pd-C bond is
the Pt-C and Pt-P coupling constants decreased upon
unsuccessful in the pyridylidene 124a, while it occurs readily
protonation. These changes were rationalized by invoking
in the pyridyl complex 123a to give 131 (see Scheme 44).
an enhanced M-C bond order. This conclusion was cor-
Instead, the pyridylidene complex undergoes a ligand
roborated by results of 1H NMR studies, which revealed a
exchange, affording the dicationic complex 132.98 Isocyanide
hindered rotation about the M-C bond in 2-pyridylidene
insertion can be initiated subsequently by the addition of a
complexes prepared by protonation, such as 124a.90,92 Steric
base. A similar reactivity pattern has been observed for the
effects might have only a minor role in explaining this
analogous nickel complexes.92
increased rigidity, because, in the precursor complexes 123a
The palladium pyridyl complex 133 that features an S,C,S-
that contain an anionic pyridyl ligand, this rotation is fast
tridentate coordinating pincer ligand has been alkylated to
on the NMR scale. Finally, the observed high-frequency shift
yield the corresponding carbene complex 134 (see Scheme
of the M-Br stretching vibration upon protonation was
45).99 UV-vis measurements reveal a bathochromic shift
attributed to a decreased trans influence of the carbene,
of the metal-to-ligand charge transfer (MLCT) band upon
compared to the anionic pyridyl ligand.90
alkylation, which has been attributed to a lowering of the
The high basicity of 2-metallated pyridines has been
π*-level. Interestingly, coordination of 133 as a metalloligand
further illustrated by the successful activation of CH2Cl2 by
to a RuCl2(η6-C6H6) fragment (complex 135) induces a
complex 129 to form the N-alkylated chloride salt 130b (see
similar MLCT band shift as methylation.
Scheme 43).94 Replacing the trans-coordinated phosphine
In some instances, alkylation of an exocyclic oxygen rather
spectator ligands by bidentate cis-chelating ligands such
than the internal heteroatom may provide a method for the
as1,2-bis(diphenylphosphino)ethane (dppe) or dimethyldithio-
formation of pyridylidene complexes.91 For example, alky-
carbamate(dmtc)doesnotinfluencethisreactivitypattern.93,95-97
lation of 136 occurs at an oxygen as the most nucleophilic
Because the 2- and 4-metallated congeners differ consider-
ably in their reactivity, the contribution of a zwitterionic Table 3. Structural Parameters of Platinum Pyridyl and
pyridinylium-type resonance structure (130′; see Scheme 43) Pyridylidene Complexes
has been suggested to be more relevant than the neutral Bond Length (Å)
pyridylidene structure 130′′.95,96 Comparison of the Pt-C
bond distances in 100, its protonated form 130a, and 130b complex d(Pt-C) d(Pt-Cl) dihedral angle, ∠(N-C-Pt-P) (deg)
is not conclusive for establishing metal-carbon π-interac- 129 1.996(8) 2.408(3) 102.47, 83.20
tions (see Table 3).94 Interestingly, the heterocycles in the 130a 1.986(9) 2.372(3) 92.86, 92.66
130b 1.956(6) 2.378(2) 90.41, 91.32
carbenoid complexes 130 are oriented almost perpendicular
Scheme 46
Figure 8. Proposed iridium structure 145, and the crystallographi-

cally determined complex 146, obtained from reacting IrCl3 and
bpy in the presence of NaOMe (bpy ) 2,2′-bipyridine).
Scheme 47 Scheme 49
site, providing an alternative approach toward the formation

of 111b (see Scheme 46).72 Examination of the molecular
structure of this pyridylidene-type complex shows significant agreement with a smaller σ-donor/π-acceptor ratio for the
alteration of the bond length within the heterocycle, indicat- 2- and 4-pyridylidene complexes as compared to the
ing castabilization of the carbene center by the nitrogen and abnormal 3-pyridylidene analogues. A similar synthetic
the exocyclic heteroatom. Similarly, the complexes 10072 and protocol has also been successfully used to prepare an
11686 have been synthesized by this route, i.e., by alkylation analogous 4-pyridylidene Ir3+ complex, which is much more
after heterocycle metallation. In all examples, the metal- stable to reductive elimination than the corresponding
bound carbon resonance shifts significantly downfield upon rhodium complex (144c).
methylation. This effect has been explained in terms of an
increased M-C bond order.
2.4.3. C-H Bond Activation
Pyridyl complex protonation has also been used to prepare
carbene complexes of gold. Depending on the metal/ligand Watts et al., in 1977, reported on the synthesis of a cationic
stoichiometry used in the preceding transmetallation, the iridium(III) complex that contained three 2,2′-bipyridine
2-pyridyl gold precursor is either oligomeric 137 (1 mol (bpy) ligands, one of which was claimed to bind in a
equiv gold) or occurs as the bis(pyridyl) aurate 139 (0.5 mol monodentate mode (145; see Figure 8).102 The exact binding
equiv gold). Both species can be protonated to produce the mode of that ligand raised a controversy,103 which was finally
monometallic monopyridylidene and dipyridylidene com- clarified by a single crystal structure determination (146; see
plexes 138 and 140, respectively (see Scheme 47).100 Figure 8).104 The structure demonstrated that this complex
While transmetallation from lithiated reagents has been contains the first, initially unrecognized, abnormal py-
used in the preparation of 2-pyridyl precursor complexes ridylidene ligand.
only, Maitlis and co-workers showed that all three pyridyl In a more rational approach, Wimmer and co-workers
isomerssand, hence, also all three pyridylidene complexessare demonstrated the successful cyclometallation of monoalky-
accessible upon decarbonylative activation of pyridine al- lated 2-pyridyl and 4-pyridyl pyridinium salts 147, using
dehydes 141 in the presence of the Rh3+ complex 142 (see tetrachloropalladate and tetrachloroplatinate precursors.105
Scheme 48). Subsequent alkylation of the pyridyl nitrogen The initially formed coordination complexes 148 were
in 143 yields the corresponding carbene complexes 144.101 isolated and converted to the corresponding metallacycles
Comparision of the spectroscopic data of the 2-, 3-, and upon heating in aqueous solutions or in the solid state (see
4-substituted pyridylidene isomers 144 with their related Scheme 49). Analysis of the resulting abnormal 3-py-
precursors 143 indicates significantly higher CO stretching ridylidene complexes 149 was hampered by their poor
frequencies for the 2- and 4-pyridylidenes only. This is in solubility in common solvents, and, perhaps as a consequence
Scheme 48
Scheme 50 chelating donor site on the functional group that is used for
pyridine N-quaternization. Using this methodology, Bercaw
and co-workers have accomplished the synthesis of N-
heterocyclic carbene Pt2+ complexes 154 when starting from
monocationic N-(2-pyridyl)-pyridinium salts 155 (see Scheme
51).110
Structural data from X-ray analysis of various carbene
complexes 154 indicate substantial bond length alteration in
of the lack of conclusive data, the carbenoid character of the heterocycles and point to partially localized double bonds
the metal-carbon bond in these complexes has not been in certain instances. In particular, such bond length alteration
discussed. seems to be dependent on the substitution pattern of the
Obviously, cyclometallation of the pyridinium salts 147 pyridinium ring. A pyridylidene-type structure featuring a
will direct the metal center to the pyridinium meta position relatively short Pt-C bond distance of 1.959(3) Å has been
to yield abnormal carbenes. In contrast, cyclometallation of proposed for unsubstituted carbenes such as 154a. While the
13
3-pyridyl pyridinium salts such as 150 may afford normal C NMR resonance of the metal-bound carbon is located at
or remote pyridylidene complexes. Reaction of 150 with the a relatively low chemical shift (δC < 180), the 1JPtC coupling
in situ formed metal precursor [Ru(bpy)2(EtOH)2](PF6)2 has constants are exceptionally large (1200-1330 Hz) and could
led to the remote isomer 151 exclusively (see Scheme 50).106 serve as a probe for the Pt-C bond order. In the para-amino-
Based on the discussion in the previous section, this reaction functionalized complex 154b, stabilization of the iminium
outcome may be understood by considering a synergistic form occurs predominantly from the NMe2 donor substituent,
interplay between the electronic preference for pyridinium rather than from the metal. Accordingly, the Pt-C bond is
C4 metallation and the steric protection of the pyridinium significantly longer than that in 154a (2.011(2) Å), and the
ortho positions by the methyl group (F-strain83). aromatic C-C bonds of the NMe2 substituted ring alternate
The pyridine-assisted cyclometallation protocol has been in length. In the isomeric 154c complex, having an NMe2
further extended to prepare Ru complexes that contain substituent in the meta position, a similar π-involvement of
terpyridinium-derived N,C,N- and N,N,C-chelating the two N atoms is not possible and no bond alteration
pyridylidenes.107-109 Particularly interesting for comparative occurs. The Pt-C bond length (2.004(6) Å) is similar to that
purposes are complexes 152 and 153, which feature remote in 154b, indicating that charge compensation in this system
and abnormal pyridylidenes, respectively (see Figure 9).109 still occurs predominantly via the NMe2 substituent rather
A distinctly different bonding situation is indicated by the than through π-backbonding from platinum. Remarkably,
NMR chemical shift of the metal-bound carbon (δC ) 183.7 however, the activation energy for rotation about the
in 152, 225.6 in 153), which could indicate a higher carbene C-NMe2 bond is considerably higher in 154c than in the
character in the complex 153. This result is further supported resonance-stabilized system 154b.
by a 50-mV anodic shift of the ruthenium(II)/ruthenium(III) Investigation of ligand substitution reactions in the 2-py-
oxidation potential in 153, compared to 152. This shift has ridylidene complexes 154 has indicated an associative DMSO
been rationalized in terms of a rise of the ligand π*-level, exchange mechanism. The exchange rate for the carbene
which is due to better π-back-donation from the metal and complex 154a is ∼3 orders of magnitude higher than for its
reflects a reduced electron transfer from the ligand to the neutral 2-phenyl pyridine analogue. Orbital considerations
metal in 153. This model is consistent with a change from of the assumed trigonal bipyramidal transition state suggest
(zwitter)ionic pyridyl-type coordination in 152 toward neutral that the exchange rate is enhanced by the presence of π-acidic
carbene-like pyridylidene donation of the ligand in 153. ligands. According to this model, the higher rate for 154a
Similar effects have been observed in the electronic spectra implies M-C backbonding in the transition state and a
of related Ru(N∧C)(bipy)2 complexes, where N∧C is an N,C- pronounced trans effect by the carbene ligand. In the ground
bidentate coordinating pyridine-pyridylidene ligand.108 Dis- state, the Pt-S bond distances are statistically identical for
placement of the alkylated nitrogen from the meta position the two complexes under discussion, thus revealing no
(abnormal carbene) to the para position (remote carbene) difference in trans influence.
induces a 38-nm hypsochromic shift of the MLCT band.106 Chelated 2-pyridylidene complexes 156 of different Group
Note that the crystallographically determined Ru-C bond 10 metals have been prepared using [M(acac)2] (M ) Ni,
distance is only slightly shorter in 153 (2.014(5) Å) than in Pd, Pt; see Scheme 51) as metal precursors.111 X-ray crystal
152 (2.033(5) Å). structures reveal a higher trans influence of the carbene
Cyclometallation of pyridinium derivatives has been donor, relative to the pyridine-type donor. The UV-vis
successfully utilized also for the preparation of normal absorption spectra of these complexes show a metal-
2-pyridylidene complexes. To increase the regioselectivity dependent MLCT absorption maximum and, hence, are
for C2-metallation, it seems advantageous to install the indicative of metal-ligand backbonding.
Figure 9. Redox-active terpyridine Ru2+ complexes featuring abnormal (152) and remote (153) pyridylidene bonding.
Scheme 51
Scheme 52 Crystallographic analysis shows a Pt-C bond distance of

1.951(9) Å, which is short for a nonchelating ligand. The
dihedral angle between the ligand heterocycle and the metal
square plane in 163 deviates remarkably (∼39°) from the
in-plane or perpendicular orientation that would be expected
for effective d-π back-donation. In solution, however,
carbene-type bonding seems to be supported by an extraor-
dinarily deshielded resonance for the metal-bound carbon
(δC ) 324.3). The addition of PPh3 cleaves the dimeric
Scheme 53 structure and gives a mixture of complexes 164 and 165.115
Complex 164 has been assigned a zwitterionic structure as
the predominant resonance form, based on the virtually
identical 13C NMR shifts of the metal-bound carbons in 164
and in the pyridyl complex 165 (δC ) 177.0 and 176.1,
respectively).
The η2-complex 166, obtained from [Os(NH3)5]3+ and a
The asymmetric palladium complex 158 has been prepared methylpyridinium salt, is metastable and undergoes a slow
from the nicotinium-derived chiral ligand precursor 157 C-H bond activation to afford the C4-bound NHC complex
under very mild conditions (see Scheme 52).112 C-H bond 167 (see Scheme 55).116 Such a transformation seems to be
activation occurs selectively at the less-acidic C4 position, unique for pyridine-derived heterocycles, because related
most likely because of effective shielding of the ortho complexes with η2-arene or η2-imidazolium ligands do not
positions by the isopropyl group. Palladation has been show similar reactivities. Interestingly, the more-acidic C2-
postulated to occur by initial formation of a palladate species position is not activated, even if C4 is protected by a methyl
and subsequent ion pairing with the cationic heterocycle prior group. This might be attributed to the steric demand of the
to Pd-C bond formation.25,26 The metal-bound carbon in 158 N-methyl group.
resonates at higher field strength (δC ) 176.2) than the Carmona and Poveda have exploited a similar F-strain83
cationic complex 108b (δC ) 197.7). This NMR shift to access pyridylidene complexes. The iridium trispyrazolbo-
difference emphasizes again the strong dependence of the rate complex, IrTp(Ph)2(N2), which contains a labile N2
carbene carbon resonance on the ligand environment of the ligand activates the C6-H bond of picoline 168a at elevated
metal. temperatures and yields the carbene complex 169a, thus
Cycloaddition of the 3,5-diphosphino-pyridine pincer inducing a formal proton shift from C6 to nitrogen to afford
ligand 159 to PdCl2(PhCN)2 proceeds smoothly in the the tautomeric carbene ligand (see Scheme 56).117 The course
absence of a base to generate the remote pyridylidene of the reaction is sensitive to the applied reaction conditions,
complex (160) (see Scheme 53).113 Formally, this reaction the substituents on the pyridine ring, and modifications to
corresponds to a pyridine tautomerization involving a 1,4- the iridium complex. For example, at 60 °C 168a was shown
migration of the proton. UV-vis spectrosopic comparison to coordinate with the N atom to the metal precursor to form
of the pyridylidene complex 160 and the deprotonated pyridyl isomer 170a, which rearranged to 169a at 90 °C. In contrast,
complex 161 indicates that protonation induces a 16-nm unsubstituted pyridine does not undergo a proton shift with
hypsochromic shift of the relevant absorption band in the the same precursor IrTp(Ph)2(N2), even at 150 °C, and
visible region. This shift has been rationalized by a reduction afforded 170d exclusively.
of the HOMO energy and thus an increase of the highest Nitrogen coordination has been partly suppressed by
occupied molecular orbital-lowest unoccupied molecular incorporating mesityl substituents in the Tp ligand of the
orbital (HOMO-LUMO) gap upon protonation, because of iridium precursor. Thus, the reaction of IrTp′(N2) with
reduced electron density at the metal center. Coordination pyridine results in the formation of a 1:1 mixture of the C-
of the pyridine nitrogen to BEt3 or to a PdCl2 fragment results and N-bound isomers (171 and 172) (see Scheme 57).118 In
in a much smaller shift of the absorption band (∆λ ) 2 nm), this situation, thermal interconversion of the two isomers has
thus suggesting a related but less-pronounced effect. not been achieved, indicating that the N-bound complex is
A similar proton migration has been observed during the probably not an intermediate during carbene formation but
metallation of ligand 162. Although this ligand seems to be rather a side product that is formed under kinetic control.
well-suited for C,N,C-terdentate pincer-type metal Crystal structure determination of different complexes 169
coordination,45b,c exclusive activation of the pyridyl C4- shows significant bond alterations within the 2-pyridylidene
position is observed. This created the dimeric complex 163, ligand, thus supporting a carbene-type Pd-C bond and a
featuring two remote NHC ligands (see Scheme 54).114 heterocycle featuring substantial diene character.117-119
Scheme 54
Scheme 55 Scheme 57
Scheme 56
Scheme 58
Deuterium labeling experiments provide evidence that the

iridium-bound mesityl substituents of the IrTp′ fragment are nium(IV) and osmium(IV) hydrides (MH2Cl2(PiPr3)2),120 and
involved in the proton shift process, possibly acting as also upon treatment of 2,3′-bipyridines with [Ir(cod)2]BF4.121
hydrogen reservoirs. Moreover, the observed depletion of In the latter case, an amide functionality as a hydrogen-bond
the deuterium content at the pyridine C3- and C4-positions acceptor group was determined to be essential for stabilizing
suggests that carbene formation at these C atoms is also the pyridylidene tautomer, as opposed to a metal-hydride
occurring. Yet, these remote products are unstable and species. These recent results indicate that such tautomeriza-
rearrange to the thermodynamically more-stable C2-bound tion reactions may have a more general scope than initially
product, which is consistent with theoretical considerations.69 believed.
Hence, in N-alkylated pyridylidenes, F-strain83 may well be A different type of C-H bond activation has been realized
a relevant driving force for remote NHC formation (i.e., for recently with the adduct 173, obtained from the reaction of
the high regioselectivity to metallate the C4-position). A the corresponding isoquinolinium salt with KOtBu or K[N-
similar tautomerization with metal involvement has been (SiMe3)2].122 Reaction with [Rh(cod)Cl]2 (see Scheme 58)
observed recently upon reaction of quinolines with ruthe- readily provides the 2-pyridylidene-type complex 174. Based
Scheme 59
Scheme 60 Scheme 62
to be remarkably stable, despite the lack of a stabilizing

on the reactivity of related adducts of 2-imidazolylidenes,123 R-heteroatom. The carbene carbon NMR resonance typically
a sequential process has been proposed, first comprising the shifts ∼50 ppm upfield upon cyclization, because of a
formation of a still-elusive free pyridylidene via the elimina- significant π-electron contribution from the aromatic py-
tion of HZ, followed by fast metal coordination. ridylium resonance form. Such a bonding model is supported
In an attempt to cyclometallate the potentially C,N- by the protolysis of the new Cr-C bond by HBF4. A
bidentate chelating ligand precursor 175 with IrCl3, complex synthetically very attractive feature of complexes 180 is their
176 has unexpectedly been isolated, along with several other propensity to transfer the pyridylidene ligand to late transition
products (see Scheme 59).124 Note that the pyridylidene-type metals, as has been illustrated recently with the preparation
ligand binds via two carbons (one of which could be of the rhodium pyridylidene complex 181 from [Rh(CO)2Cl]2
considered a normal carbene) to the metal center. While such and 180a.128 Comparison of the low CO stretching frequen-
complexes may be of interest (for example, as novel light- cies of the cis isomer (average νCO ) 2014 cm-1) with related
emitting materials), further studies are required to devise a complexes (Vide supra) places this 4-pyridylidene system
rational synthetic protocol. among the strongest carbene-type donor ligands known to
date.
2.4.4. P-C Bond Activation Cycloaddition has also been performed with R,β-unsatur-
ated imines, which does not require the installation of the
The transfer of an organic substituent from a phosphine
final heteroatom in the Fischer carbene. For example, the
ligand onto the central metal in the presence of a nucleophile
anionic carbene complex 182 reacts with the azabutadiene
is a well-known decomposition pathway in homogeneous
183 to afford the 2-pyridylidene manganese(I) complex 184
catalysis.125 In organometallic synthesis, however, this
(see Scheme 62).129 Analogously, 2-pyridylidene W0 com-
reactivity has not been much exploited thus far. The neutral
plexes have been prepared.130 The molecular structure of
2-pyridylidene complex 178 has been obtained serendipi-
complex 184 displays bond lengths that indicate substantial
tously when heating the palladium dichloride complex 177,
electronic delocalization within the pyridylidene ring. No-
which is comprised of 2-pyridyl-substituted phosphines in
tably, the carbonyl 13C NMR shift, as well as the IR
methanol (see Scheme 60).126 Comparison of the crystallo-
absorption frequencies, are almost identical to those observed
graphically determined Pd-Cl bond lengths in 178 indicates
in the analogous 2-thiazolylidene complex.74 This suggests
that the trans influence of the carbene donor is slightly
similar donor properties of these two carbene systems.
stronger than that of the phosphine.
The dichotomy in representing Fischer carbene and NHC
complexes is perhaps most clearly illustrated in the reaction
shown in Scheme 62: while the M-C bond is not altered
Pyridylidene complexes can be synthesized by modifying considerably during the heterocycle formation, the different
existing coordinated carbenes. For example, Aumann and manners of representation for the complexes 182 and 184
co-workers succeeded in reacting the amino-functionalized imply a substantial change in the bonding. This dichotomy,
Fischer carbene complex 179 with alkynes to yield 4-py- grown historically, along with the borderless transition from
ridylidenes such as those in complexes 180 (see Scheme purely M-C single bonded carbenes to increasing M)C
61).127 These remote carbene complexes were determined double bond character, both in Fischer carbene and NHC
Scheme 61
Scheme 63
Scheme 64 complex decomposition. Although, apparently, steric bulk

and rigidity is essential to stabilize 14e complexes, certain
catalytic applications improve when the substituents at this
R-position are flexible (cf. section 5). Moreover, the coor-
dinatively saturated rhodium complex 188b is structurally
related to other rhodium carbene complexes and allows
comparison of ligand effects. Based on CO stretching
frequencies in the corresponding RhCl(CO)2 complexes,
complexes, makes a consistent representation of the formulas these CAACs are stronger donors than classical NHCs, yet
in this review impossible. Therefore, we have used the single weaker than C4-bound abnormal imidazolylidenes. This
bond representation for all NHC complexes that have some outcome has been attributed to a combination of relatively
degree of aromatic character, whereas for Fischer carbene strong σ-donor and weak π-acceptor properties of CAACs.
complexes, and also for saturated N-heterocyclic carbene Flexible substituents such as the cyclohexyl group in 186b
complexes, discussed in the subsequent section, a double- provide facile access to bis(carbene) complexes of gold via
bond representation has been adopted. It is our understanding homoleptic rearrangement from (CAAC)AuCl to
that the different representations heavily overemphasize the [(CAAC)2Au]+ and [AuCl2]-.134 A similar rearrangement can
effective differences in bonding. be prevented using bulky ligands such as 186a or 186c,
which comprise an adamantyl-derived motif to stabilize the
2.5. Complexes Comprising Cyclic (Amino)(Alkyl) gold carbene complex 189. Remarkably, abstraction of the
or (Amino)(Ylide)Carbenes metal-bound halide in 189 affords 190, which is a rare
example of a stable arene Au+ π-complex (see Scheme
2.5.1. Coordination to Free Cyclic (Amino)(Alkyl)Carbenes 65).135
Based on the successful preparation of free (amino)(alkyl)- In an attempt to synthesize Grubbs-type catalysts featuring
carbenes (AACs),9 Bertrand and co-workers pursued the CAACs, the carbenes 191 were reacted with the Ru precursor
synthesis of stable cyclic (amino)(alkyl)carbenes (CAACs) complex 192 (see Scheme 66).136 However, an unexpected
and their transition-metal complexes. Deprotonation of a air-sensitive product 193 was obtained, in which the phos-
cyclic aldiminium salt quantitatively afforded the stable phine rather than the pyridine was replaced by the carbene
carbene 186a.131 Subsequent metal coordination gave the ligand. Based on the same principle, the related Grubbs-
complexes 185 and 187 (see Scheme 63).132 The Rh center Hoveyda catalyst 194 was successfully prepared from the
spontaneously lost one CO ligand upon carbene bonding to corresponding phosphine ruthenium precursor.
afford 185 complex as a rare 14e species. The 14e palladium
carbene complex 187 was accessible by coordination to 2.5.2. Oxidative Addition
[Pd(allyl)Cl]2 and subsequent Ag+-mediated halide abstrac- In analogy to other less-stabilized NHC complexation
tion. In contrast to previous attempts to prepare similar 14e procedures (Vide supra), oxidative addition was also suc-
complexes with 2-imidazolylidenes,133 the compounds 185 cessfully applied for the preparation of a CAAC complex.
and 187 were stable and could be crystallized. Structural Starting from the chloride salt precursor 195, oxidative
analysis indicated that at least one of the axial C-H bonds addition to Pd0 occurred smoothly and afforded the neutral
of the menthyl ring was involved in an agostic interaction. complex 196 (see Scheme 67).137 Both chlorides are coor-
The relevance of agostic interactions in stabilizing these dinated to the Pd center in the product and, in contrast to
coordinatively unsaturated species has been probed by the pyrazolylidene analogue 73 (cf. Scheme 26), the halides
modifying the substituents in a position R to the carbene adopt a mutual trans disposition.
carbon. Replacing the menthyl moiety with a sterically more
flexible cyclohexyl group 186b, which can twist away from 2.5.3. C-H Bond Activation
the metal coordination sphere, results in the exclusive
formation of square-planar 16e complexes 188 (see Scheme Direct C-H bond activation has been explored little in
64).131 Attempts to remove one of the ligands induced the synthesis of carbene complexes that comprise saturated
Scheme 65
Scheme 66
Scheme 67 Scheme 70
Scheme 68

heterocycles. In an unusual approach, the 14-electron species Heterocyclic ring formation from Fischer-type allenylidene
197 has been used to geminally dehydrogenate pyrrol, thus complexes provides a versatile pathway for the synthesis of
generating the carbene complex 198 (see Scheme 68).138 The nonconjugated heterocyclic carbene complexes. This route
formation of RuH(H2)Cl(PiPr3)2 as a side product is ef- is related to the method used in the preparation of pyra-
ficiently suppressed in the presence of t-butyl ethylene as a zolylidene complexes (cf. Scheme 34). For example, the
H2 scavenger. Interestingly, piperidine undergoes a similar reaction of the allenylidene complex 202 with hydroxylm-
double dehydrogenation only with the osmium analogue of ethylamine furnishes the unsaturated isoxazolinylidene com-
197, OsHCl(PiPr3)2, but not with the Ru complex itself. plex 204 (see Scheme 70).141 With diamines, complex 203
Apparently, subtle steric differences in the heterocycle have is obtained and acid catalysis is required to promote
a pronounced influence on this reaction. cyclization of the carbene ligand.66,142 The ring closure has
A similar reactivity has also been observed with the only a minor effect on the IR spectroscopic properties of
iridium complex [Ir(H)2(PPh3)2(acetone)2]. Double sequential the CO ligands (see Table 4). This result indicates similar
R C-H bond activations in 199 produce the carbene complex donor properties and bonding characteristics for the saturated
201 (see Scheme 69).139 In a coordinating solvent such as pyrazolinylidene in 205 and related acyclic Fischer ami-
acetone, the second R-elimination is reversed and carbene nocarbene complexes. According to the CO stretching
insertion into the Ir-H bond affords the alkyl iridium vibrations, pyrazolylidenes are slightly weaker donors than
complex 200. Such solvent-induced toggeling between their unsaturated pyrazolylidene analogs (cf. 90 in Scheme
carbene and alkyl bonding modes may provide access to 34), yet they are stronger than the corresponding isoxazoli-
useful (catalytic) applications, perhaps involving hydrogen- nylidene ligand in 204, although the differences are small.
transfer reactions. Similarly to ring-expanded classical NHCs The reactivity differences are more significant: in contrast
(which are comprised of two stabilizing heteroatoms bound to the 90 complex, the pyrazolinylidene ligand in complex
to the carbene carbon),140 an increase of the ring size of the 205 is inert and not transferable to late transition metals.
carbene in 201 induces a marked downfield shift of the Cyclic (amino)(alkyl)carbene complexes related to 204 and
carbene carbon 13C NMR resonance (δC ) 258.3 in 201a, 205 have been synthesized via various different methods,
δC ) 262.2 in 201b, and δC ) 270.7 in 201c), suggesting a including CdO activation in lactames, alkylation of coor-
higher degree of Fischer carbene character in the ring- dinated isocyanides, and heteroatom substitution in oxacy-
expanded systems. cloalkylidene complexes of chromium with an NH unit.
Scheme 69
Scheme 72
Figure 10. Representative examples of N-heterocyclic carbene

complexes that may be classified either as cyclic (amino)(alkyl)-
carbene or as Fischer carbene complexes, made by lactam CdO
activation (206), isocyanide alkylation (207), and substitution of
the heteroatom in cyclopentenylidene complexes (208).
Scheme 71
Scheme 73
Representative products of these reactions are shown in

Figure 10 (206-208).143 Because of their chemistry, these
complexes are generally called Fischer aminocarbene com-
plexes and, therefore, are not treated any further here;
Fischer-type carbene complexes have been reviewed else-
where.144
The observed CO frequencies in the IR spectra of 213b
2.5.5. (Amino)(Ylide)Carbenes (average νCO ) 2012 cm-1), 214 (average νCO ) 2014 cm-1),
Recently, an important variation within NHC chemistry and 215 (average νCO ) 2009 cm-1) indicate a remarkably
was revitalized by incorporating heteroatom stabilization by high electron-donating ability of these carbene ligands (cf.
virtue of an exocyclic ylide residue. Ligands such as νCO ) 2036 cm-1 for the 2-imidazolylidene analogue), as
(amino)(ylide)carbenes (AYCs) had originally been prepared also inferred from the chromium complex 210. The data
from phosphonium-functionalized isocyanides such as 209 further suggest that the donor ability and bonding features
by metal coordination and subsequent base-induced ring of the carbene may be tunable through a judicious choice of
closure (see Scheme 71).145 Electrochemical studies on the the ylide moiety and heterocycle backbone. However, further
formed complexes 210 suggested a weak yet noticeable investigations are warranted to transform these isolated
correlation of the electron density at the metal with the observations into clear and useful trends. Calculations have
substituents at the phosphorus ylide functionality. indicated that the increased electron donor character is
A new synthetic route toward such AYC complexes predominantly a result of strong σ donation, rather than weak
involves cyclization prior to metal coordination. The phos- π-acceptor properties.
phonium-substituted indol 211 (Scheme 72) has been depro- A special type of ylide-stabilized carbene ligand consists
tonated with a sterically demanding base such as MesLi or of C-ylides comprising a carbene as substituent. While
K[N(SiMe3)2]. The anticipated free carbene readily coordi- metallation of the iminium salt 216 via intermediate forma-
nates to a suitable Pd2+ or Rh+ complex to form the tion of a free carbene has failed thus far, cyclometallation
complexes 212 and 213, respectively.146 Employing such using Pd(acac)2 at elevated temperatures produces complex
methods, complexes that contain AYCs stabilized by an 217 (see Scheme 73).147
internal sulfonium-ylide 214 or composed of a pyrazol- An interesting variation within the theme of exocyclic
derived heterocycle 215 have also been prepared.147 carbene stabilization has been exploited by inserting a thiene
Table 4. Spectroscopic Data for Chromium Pentacarbonyl Complexes Containing Carbene Ligands
type of carbene complex δC (carbene) νCO (cm-1) reference
3-pyrazolylidene 90 190.8 2049, 1938, 1926 65a
3-pyrazolinylidene 205a 241.6 2052, 1966, 1926 66
3-oxazolinylidene 204a 222.2 2058, 1973, 1932 141
4-pyridylidene 180a 236.2 2043, 1919 127a
4-pyridylidene 180b 235.0 2043, 1919 127a
4-pyridylidene 180c 243.2 2043, 1919 127a
4-pyridylidene 180d 225.6 2043, 1923 127a
acyclic (amino)(alkyl)carbene 206 265.1 2058, 1978, 1940, 1939 143a
cyclic (amino)(alkyl)carbene 208 271.2 2054, 1965, 1927 143c
cyclic (amino)(vinyl)carbene 225 249.2 2044, 1956, 1918 65b
cyclic (amino)(vinyl)carbene 227a 231.4 2047, 1919, 1902 150
cyclic (amino)(vinyl)carbene 227b 229.9 2048, 1920, 1903 150
cyclic (mercapto)(vinyl)carbene 226 270.9 2044, 1962, 1924 65b
acyclic (amino)(vinyl)carbene 203a 250.1 2052, 1970, 1928 142
acyclic (alkoxy)(vinyl)carbene 179a 290.7 2050, 1936, 1930 127b
Scheme 74 Scheme 76
Scheme 77
Scheme 75
The six-membered analog of the heterocyclic carbene in

225 has been prepared via an unusual rearrangement in the
pyrazolylidene complex 90 (see Scheme 77).150 Deprotona-
tion with BuLi occurrs selectively at the N-methyl group that
moiety between the metal center and the heterocycle (see
is situated remote from the carbene C atom and induces a
Scheme 74).61,148 Based on IR and NMR data of the
rearrangement to the six-membered ligand. Subsequent
complexes 220 and 221, the metal-carbon bonds in the
protonation or alkylation yielded complex 227. According
former compound lay claim to a significant π-contribution
to IR spectroscopic measurements (Table 4), the six-
from the metal, whereas in complex 221, the cationic charge
membered carbene seems to be a stronger donor than its
is much more localized on the nitrogen-containing hetero-
seven-membered congeners.
cycle than toward the metal, suggesting a preponderance of
A different synthetic approach involving cyclization at the
a zwitterionic structure.
metal has been utilized for synthesizing the palladium
The concept of AYCs has recently been expanded to carbene complex 229 (see Scheme 78). The addition of
include chelating ligands by resorting to the base sensitivity t-butyl isocyanide to the ortho-xylyl complex 228 results in
of the ylide moiety in the free carbenes.146 When using MeLi the formation of a heterocycle and affords the cationic
(2 mol equiv) as a base for deprotonation of the pyrrol carbene complex 229.151 Cyclization is probably initiated by
phosphonium ylide 222, Bertrand and co-workers have isocyanide insertion into the Pd-C bond of 228, followed
observed the substitution of a phenyl residue by a CH2Li by nucleophilic substitution of the benzylic chloride to form
unit, thus yielding the lithium carbene species 223 (see the ring. The acidic proton in a position R to the carbene
Scheme 75).149 Mechanistic investigations suggest a stepwise carbon in 229 can be abstracted in a reversible reaction by
process with, first, the addition of CH3- anion to the relatively mild bases, such as 1,8-diazabicyclo[5.4.0]undecene
phosphonium unit and the subsequent base-mediated elimi- (DBU), to afford the neutral vinyl complex 230. Remarkably,
nation of Ph-H to form 223. Transmetallation with Rh+ and the NMR shift of the metal-bound carbon barely changes
Pd2+ precursors provided the new complexes 224, both upon deprotonation (∆δC ≈ 6), despite the significant
comprising a monoanionic C,C-bidentate coordinating AYC rehybridization and conformational changes that are associ-
ligand. ated with this reaction. In the 229 complex, the heterocycle
is forced into a boat conformation, whereas, in 230, it is
2.6. Miscellaneous N-Heterocyclic Carbenes with essentially planar.
Low Heteroatom Stabilization
Seven-membered heterocyclic carbenes with only one
3. Carbenes or Zwitterionic Ligands?
stabilizing heteroatom adjacent to the carbene carbon have The question of carbene (or carbenoid) character in so-
been prepared by cycloaddition of a diamine or an aminothiol called metal carbene complexes and, more particularly, the
to the allenylidene 91, thus affording complexes 225 and importanceofM-Ccarbene π-interactionhasbeenaddressedsalbeit
226, respectively (Scheme 76).65b IR spectroscopic analysis not always satisfactorilyssince the characterization of the
(Table 4) revealed that the seven-membered carbenes transfer first Fischer-type carbene complexes.152 Aminocarbene com-
slightly less electron density onto the metal than a normal plexes of Group 6 metals have become prime examples to
pyrazolylidene ligand (such as 90, cf. Scheme 34). This trend illustrate the bonding behavior of such complexes, using two
is not reflected in the corresponding 13C NMR data. extreme canonical representations (see Scheme 79).
Furthermore, related absorption data for complexes 225 and The relevance of the zwitterionic form X′ is readily
226 suggest that the type of heteroatom has only a minor appreciated by the chemical nonequivalence of the two
influence on the donor properties of these ligands. N-bound R groups in the 1H and 13C NMR spectra.
Scheme 78
Scheme 79 Scheme 80
In NHC complex chemistry, the prevalence of metal-ligand Scheme 81

π-interaction has become a controversial and still unsettled
issue,153 and with the current boom of homogeneous gold
catalysis in organic synthesis, the importance of π-interac-
tions is again being discussed.154 With the growing relevance
of abnormal and remote NHC complexes, the nature of the
synergistic metal-carbene bonding is addressed continu-
ously. The biggest impediment to clearing up this problem
is probably the general insensitivity of the metal-carbene
bond length to small changes in bond order. However,
Bercaw and co-workers indicated that such changes can be
evoked by providing competing possibilities for diminishing
the positive charge on the carbene C atom.110 Thus, variations
in the contributions of limiting structures can be measured.
Various other physical methods have been utilized to study
the attachment of nonclassical NHCs to metal fragments.
While IR spectroscopic measurements provide a satisfactory The two largest groups of compounds treated in this review
method for quantifying the donor power of ligands trans to are the abnormal 4-imidazolylidenes and the pyridinium-
CO (Tolman parametrization), such analyses do not clearly derived carbene complexes. For the former group, it is not
allow for dividing bonds into σ- and π-contributions. Often, possible to write formally neutral valence-bond contributing
the chemical shift of the carbene C nucleus in 13C NMR structures wherein the metal participates in π-bonding with
spectroscopy has been correlated with the carbene character. the carbene ligand. The formal positive charge is shared
Such data must be considered with utmost care, because the between the two nitrogens, whereas the negative charge is
NMR resonance is affected by multiple components. Factors directed toward the metal center and the metal-bound carbon
such as the position of the heteroatom(s), the substitution (see Scheme 80). Analogous considerations hold for com-
pattern, contribution from aromaticity, steric constraints, or plexes that contain 4-pyrazolylidene ligands (cf. O in Figure
the nature of cis-positioned ligands affect the chemical shift 4). Nevertheless, with six π-type electrons available, potential
substantially and limit the use of NMR data for bonding- M-C π-interactions involving a π* molecular orbital (MO)
mode analysis. Often, correlation of the 13C NMR data with of the heterocyclic ring may, of course, not be excluded.37
other analytical techniques is relatively poor (cf. Tables 2 All studies consistently indicate that the ligands belonging
and 4), thus indicating that such data must be critically to these classes are pre-eminently very strong σ-donors and
evaluated. Ideally, comparisons should concentrate on ho- weaker π-acceptors than their normal isomers, and these
mologous series of compounds or related structural isomers. complexes also exhibit significantly lower 13C chemical shifts
This is also the situation for metal-carbon coupling constants than the 2-imidazolylidenes.
1
JMC. Often they do not follow a consistent trend56 and their Pyridinium-derived carbenes can be of the normal non-
discussion has been contradictory.93,110 remote Z, abnormal remote AA, and normal remote AB type
Inherent in the association of a larger 13C chemical shift (cf. Scheme 36). The most important contributing neutral
with more “carbene character” is the assumption that metal- resonance structures are illustrated in Scheme 81.
to-carbene π-back-donation does not effect the same amount Theoretical studies on the metal-carbon bond by energy
of carbon shielding to the donor C atom as participation in decomposition analysis revealed that, in all investigated NHC
π-bond formation within the heterocyclic ring. In the complexes, this bond is predominantly electrostatic.14,37,77,78,84
outstanding work of Tanaka and co-workers,106,108,109 such Only about one-third of the bonding energy has been
conclusions are corroborated by significant shifts of the metal attributed to covalent interactions. This portion can be further
oxidation potentials, as a consequence of the expected separated into ∼20 ( 5% π-bonding and 80 ( 5%
difference in charge transfer. The sensitivity of the chemical σ-interactions. Such a bonding situation is highly reminiscient
shift of the C donor atom toward the effect exercised by of that in amino carbene complexes of the Fischer type.85
ancillary ligands is probably most dramatically illustrated The exact σ/π bond contribution depends on the type of
by the work of Rourke’s group. Modification of the ligands carbene and also on the electronic configuration at the metal
in the complexes 163-165, accompanied by changes in center. In contrast to the composition of the M-C bond, the
structure and by steric effects, induces a shift of >100 ppm bond strength is highly sensitive to the number of stabilizing
(cf. Section 2.4.3).115 heteroatoms and their position relative to the carbenoid
Table 5. Catalytic Activity of Complexes with Less-stabilized Carbene Ligands
type of carbene ligand catalyst precursor catalyzed reaction reference(s)
C4-bound imidazolylidene 13, 55a Mizoroki-Heck 24, 51
C4-bound imidazolylidene 13, 235, 236 Suzuki-Miyaura 24, 164
C4-bound imidazolylidene 231 biaryl coupling 162
C4-bound imidazolylidene 236 direct hydrogenation 35
C4-bound imidazolylidene 31, 238, 240 transfer hydrogenation 34, 39
C4-bound imidazolylidene 245 hydrosilylation 170
C3-bound pyrazolylidene 73 Mizoroki-Heck 57

C3-bound pyrazolylidene 69, 70 transfer hydrogenation 34
C4-bound pyrazolylidene 233 Suzuki-Miyaura 58
C2-bound pyridylidene 156b, 232 Mizoroki-Heck 111

C2-bound pyridylidene 104b Suzuki-Miyaura 77
C2-bound pyridylidene 106a Kumada-Corriu 80
C2-bound pyridylidene 174 hydrosilylation 122
C3-bound pyridylidene 112b Suzuki-Miyaura 77
C4-bound pyridylidene 111b Mizoroki-Heck 77
C4-bound pyridylidene 108b, 158 Suzuki-Miyaura 77, 112
C4-bound pyridylidene 110a Kumada-Corriu 80
cyclic (amino)(alkyl)carbene 188a R-keto arylation 131

cyclic (amino)(alkyl)carbene 194 olefin metathesis 136, 171
carbon. Calculations have predicted that adjacent N atoms recent study, Wolf and Plenio succeeded, for the first time,
reduce the energy level of the σ lone pair orbital of the ligand in demonstrating a linear relationship of the νCO frequencies
and thus the bonding energy.82,84 Hence, the higher the between complexes of the type IrCl(CO)2(L) and
stability of the free carbene, the weaker the metal-carbon RhCl(CO)2(L).160 Several new rhodium (I) and iridium (I)
bond in the complex. The reactivity patterns illustrated in complexes will be required to demonstrate the validity and
the previous sections indicate, however, that this generaliza- the sensitivity of the established correlation of the two scales
tion needs considerable caution. For example, reductive and to identify potential limitations. It is conceivable that
eliminations appear to be much easier in C4-bound imida- stereoelectronic effects influence the cis-located CO ligand
zolylidenes than in their C2-bound congeners.7 Similarly, the to such an extent that the IR frequencies may reflect steric
Ag-C bond in C4-bound imidazolylidene and triazolylidene effects of the ligand and not only electronic parameters.
complexes seems considerably less stable than the analogous Therefore, caution is required in using CO stretching
bond in Ag complexes of 2-imidazolylidenes.20,28 frequencies as a unifying concept for probing the ligand
donor properties, in particular when comparing sterically very
4. Donor Properties of the Ligands different carbene systems. For example, the size of the
heterocyclic carbene (5-membered vs 6-membered) and the
The overall donor ability of ligands has generally been presence and nature of substituents (e.g., protons ortho to
characterized according to two complementary scales: Tol- the metallated carbon in many 4-pyridylidene ligands vs alkyl
man’s electronic parameters (TEPs)29 and Lever’s electronic or aryl substituents in 2-imidazolylidenes) may induce a shift
parameters (LEPs).155 A recent study successfully illustrated of the CO stretching frequencies that cannot be attributed
that the two parametrization systems are consistent and can exclusively to electronic effects.
mutually be translated.156 The TEP of a given ligand is
Notably, the second parametrization of ligands by elec-
determined by IR spectroscopy, using the pertinent CO
trochemical methods and leading to LEPs has only rarely
stretching vibrations. This method was developed originally
been used in carbene chemistry.13,161 While electrochemical
for nickel complexes, Ni(CO)3(L), although it has recently
methods require more sophisticated set-ups and are more
been adapted to other metals as well. Specifically, it has been
laborious, they may become relevant with ligand systems
shown that the associated TEP of ligands L in complexes of
where IR absorption spectroscopy is not suitable.41,132,158
general formula IrCl(CO)2(L) can be determined by using
linear regression methods.53 Hence, the CO stretching
frequency, taken as an average of the asymmetric and the 5. Catalytic Applications
symmetric vibration, offers a direct probe for the donor The activity of transition-metal complexes in homogeneous
ability of the corresponding ligand. This method has been catalysis is, by and large, a function of the ligands that are
extensively used in NHC chemistry, and pertinent data are attached to the metal center. The influence and electronic
available also for many abnormal carbene ligands. impact of nonclassical carbene ligands on metal centers has
A similar correlation has been derived for the TEP and been investigated in many situations, which are summarized
the average of the CO stretching vibrations in the complexes in Table 5. Not unexpectedly, Pd complexes have received
Cr(CO)5(L), which is particularly useful for NHC subclasses the most attention, although, lately, also catalytic applications
prepared from Fischer carbene complexes.157 In contrast, of Ni, Rh, and Ru complexes have been reported.
donor quantification based on RhCl(CO)2(L) complexes have
long been on weak grounds, despite the fact that many studies 5.1. Carbon-Carbon Cross-Coupling Reactions
use this RhCl(CO)2 synthon for the assessment of donor
ability.41,56,131,132,158,159 To the best of our knowledge, the Palladium carbene complexes have been used in a variety
correlation between the TEP (or LEP) and the CO vibrations of C-C bond-forming reactions. For example, the C4-bound
in these Rh complexes has not yet been established. In a carbene complex 13 is an efficient catalyst in the Heck
Scheme 82
Scheme 83 However, it is a considerably more-active complex than

related Pd complexes that contain 2-imidazolylidene ligands
with similar steric bulk.
Along these lines, Heck arylation of olefins with the
abnormal imidazolylidene carbene complex 55a as a catalyst
has been tested in the presence of excess Hg0.49 A marked
decrease in catalyst activity was noted, which indicates a
mechanism that involves, at least in part, heterogeneous
palladium. In this case, the main function of the carbene
ligand seems to be the controlled release of palladium from
the complex. Ideally, the rate of palladium dissociation is
fast enough to achieve high turnover frequencies (TOFs),
yet slow enough to prevent metal aggregation and the
formation of palladium black. Similar conclusions have been
drawn from mechanistic investigations using the pyridylidene
complex 232 in Heck-type coupling reactions.99b
Suzuki-type aryl cross-coupling reactions have been tested
with a variety of catalysts (see Scheme 84). Given the fact
that very low catalyst loadings are usually sufficient to
catalyze this reaction,163 good catalytic activities are not very
surprising. Notably, the kinetic reaction profile of some
catalytic runs (e.g., 111b, cf. Scheme 83) indicates remark-
ably high initial TOFs, followed by a sharp reduction of the
olefination of aryl bromides.24 In contrast, the corresponding conversion rates.77,78 These features, combined with the high
normal analogue 12 is virtually inactive under identical reaction temperatures, may point to ligand dissociation and
conditions. Remarkably, when preparing the catalyst in situ formation of (colloidal) Pd0, although palladium black has
with a mixture of precursor imidazolium salt and [Pd(OAc)2] not been observed at the end of the reaction.
in the presence of Cs2CO3, i.e., conditions that are used to The cationic abnormal carbene complex 233, derived from
synthesize normal 12, the catalytic activity is almost identical the neutral complex 75a (cf. Scheme 27), catalyzes biaryl
to that of 13. Similar results were obtained for the cross-coupling reactions at room temperature and in aqueous
Suzuki-Miyaura cross-coupling of aryl chlorides with aryl- media.58 Good yields were obtained for activated aryl
boronic acids. bromides, and at 80 °C also for deactivated aryl bromides.
A close analogue of 13, which comprises diisopropylaryl An appreciable 37% conversion of aryl chlorides was
rather than mesityl wingtip groups 231, has been used in recorded, which may be further improved by suitable ligand
the intramolecular arylation of aryl chlorides (see Scheme tuning and catalyst optimization.
82). A series of related complexes 234-236 (see Scheme 84)
In these reactions, however, the abnormal complex is that contain a thiazolylidene ligand, featuring either normal
significantly less efficient than classical NHC-palladium or abnormal carbene bonding, has been tested in Suzuki
catalysts or mixtures of [Pd(OAc)2] and imidazolium salts.162 cross-coupling, using phenylboronic acid and bromoac-
Mechanistic investigations suggest that the catalytically active etophenone as an activated substrate (cf. Scheme 84, X )
species may also be formed from palladium black and Br, R ) COCH3).164 Reactions performed at 70 °C provide
imidazolium salts. These observations could point to a a trend in activity that decreases slightly in the following
heterogeneous mode of action. order:
Various pyridinium-derived Pd complexes have been used C2-bound complexes 234 >
in Mizoroki-Heck olefin arylation (see Scheme 83). Com- C4-bound complexes 235 > C5-bound complexes 236
mon to all catalysts is their relatively low reactivity toward
aryl chlorides and the fact that high reaction temperatures This sequence suggests that abnormal bonding, such as that
are usually required for appreciable conversions. For ex- in 235 and 236, is disadvantageous, whereas steric bulk in
ample, the cationic pyridylidene complex 111b couples at least one ortho position is beneficial. Notably, time-
activated and deactivated aryl bromides with butylacrylate dependent monitoring of the catalytic reaction does not
at 145 °C.77,78 The catalyst is considerably more active than indicate a significant decrease of activity in any of the three
the analogous normally C2-bound imidazolylidene complex. systems.
In contrast, the palladium 2-pyridylidene catalyst 156b is A similar comparison of the influence of different carbene
not significantly faster in catalyzing Heck-type olefin ary- bonding modes has been performed with pyridylidene Pd
lation than Pd2(dba)3.111 Similarly, the pyrazolylidene com- complexes 104b, 108b, and 112b (cf. Figure 5), which is
plex 73 has shown relatively low catalytic performance.57 comprised of a normal C2-bound carbene, a remote (and
Scheme 84
Scheme 85 nickel(0) form. A related C2-bound bis(2-imidazolylidene)

nickel complex appeared to be virtually inactive in this cross-
coupling reaction.
Saturated cyclic (alkyl)(amino)carbenes have been suc-
cessfully used as catalysts for the R-arylation of propiophe-
nones (see Scheme 86).131 The catalytic performance of the
Pd center is strongly dependent on the substitution pattern
at the R-carbon of the catalyst. Flexible yet sterically
demanding substituents, such as the cyclohexyl group in
188a, seem to be particularly beneficial, because this group
can easily switch between different conformations.
5.2. Hydrogenation and Hydrosilylation Reactions

Apart from C-C bond-forming reactions, certain NHC-
normal) C4-bound carbene, and an abnormal (and remote) metal complexes are also useful catalysts for hydrogenation
C3-bound carbene, respectively. Initial activity of the normal reactions. Direct hydrogenation under mild conditions has
pyridylidene complexes 104b and 180b in the Suzuki cross- been catalyzed by the cationic Pd(dicarbene) complex 237
coupling are identical, whereas the abnormal pyridylidene (see Scheme 87).35 The activity of this complex is signifi-
complex is slightly less active. In terms of stability, the cantly higher than that of its C2-bound analogue, possibly
catalysts generated from remote pyridylidene complexes because of the higher electron density at the metal center,
108b or 112b are superior to the ortho-substituted py- which may facilitate the oxidative addition of H2 during the
ridylidene system derived from 104b, which seems to catalytic process. Mechanistic studies have also indicated a
deactivate after a few hours. heterogeneous mode of action of the catalyst due to the
High temperatures are required for Suzuki cross-coupling formation of nanoparticles.167 Particle formation may be
reactions catalyzed by complex 158, which is comprised of stimulated under the mildly reducing conditions during
a chelating remote pyridylidene-type ligand.112 Interestingly, hydrogenation.168 However, these findings do not rule out
the activity of this complex is comparable to in situ-generated several modes of actions that operate in parallel, and, at
catalysts from Pd(OAc)2 in pyridinium-based ionic liquids.165 present, it is difficult to draw a definite conclusion.
These results could suggest that the active species in both
processes is similar. Recently, related Rh complexes such as 238 have been
The cationic pyridylidene nickel(II) complexes 104a-111a used as catalysts for the transfer hydrogenation of ketones,
have been investigated in the Kumada-Corriu cross-coupling using i-PrOH as a hydrogen source (see Scheme 88).39 While
of Grignard compounds with aryl halides (see Scheme 85).80 activities are acceptable (TOF values at 50% conversion are
The catalytic activity shows a considerable dependence on >200 h-1), it is noteworthy that the corresponding C2-bound
the substitution of the heterocycle, which, therefore, offers Rh complexes are virtually inactive in catalyzing such
efficient tuning possibilities. With the 2-pyridylidene complex hydrogen-transfer reactions. This behavior may again be a
106a and the remote carbene complex 110a, a catalytic direct consequence of the electronic differences imposed by
performance has been achieved that compares well with the the C4-bound imidazolylidene ligands, which provide higher
most active system known to date, viz, a mixture of electron density at the metal center. Stronger donation is
IMes · HBF4 and [Ni(acac)2].166 These pyridylidene Ni sys- supposed to weaken the rhodium-alkoxide bond, thus
tems also allow for the transformation of deactivated aryl facilitating β-hydrogen elimination and product release.
chlorides, with good conversions. A color change was In a recent study, Peris and co-workers have compared
observed at the onset of the reaction, which may point to a different normal and abnormal carbenes in the β-alkylation
reduction of the catalyst precursor into a more active of secondary alcohols (see Scheme 89).34 This reaction is
Scheme 86
Scheme 87
Scheme 88
Scheme 89
Scheme 90
believed to involve a cascade process that is comprised of
alcohol dehydrogenation, subsequent aldol condensation, and,
finally, hydrogenation of the R,β-unsaturated ketone.169 The
cationic bis(pyrazolylidene) complex 70 seems to be most
efficient and converted different secondary methyl alcohols
to their higher homologues within 10 h or less. When using
complexes with only one carbene ligand, reaction times
generally increase in the sequence
pyrazolylidene 69 < abnormal carbene 239 < isoquinolylidene ligand. Further catalyst optimization is
normal carbene 240 required to make this process competitive and synthetically
The observed conversions suggest that strong σ-donation, useful.
which is inherent to abnormal carbenes and also to pyra- Studies of catalytic hydrosilylation were also undertaken
zolylidenes, enhances the catalytic activity of the system. by Cavell and co-workers using a catalyst generated in situ
from Pt(nbe)3, KOtBu, and different imidazolium salts.7c,170
Related to the aforementioned hydrogenation reactions, the The catalyst system based on the 2H-imidazolium salt 244
pyridylidene Rh complex 174 has been reported to be an is the most active one and gives predominantly the hydrosi-
active catalyst for the hydrosilylation of ketones (see Scheme lylated product 241 from the reaction of styrene with HSiEt3
90).122 After hydrolysis of the silyl ether, the corresponding (see Scheme 91). Remarkably, with the 2-methylated imi-
alcohols are obtained with conversions of up to 50%. This dazolium salt 245, the activity is comparable, yet dehydro-
reaction sequence provides an indirect and selective route genative silylation is the major pathway and affords pre-
for carbene metal-mediated hydrogenation of ketones. The dominantly 243 as product. This product is thought to be
catalytic activity of complex 174 appears to be very sensitive generated by a β-hydrogen elimination step, following the
to the substitution pattern on the benzene fragment of the insertion of styrene into a Pt-Si bond. Apparently, abnormal
Scheme 91
Scheme 92 Table 6. Comparison of Catalytic Activities of Ru-Carbene

Complexes in Ring Closing Olefin Metathesis
R)H R ) CH3
catalyst
conversion time temp conversion time temp
194a 97% 3.3 h 60 °C 95% 20 h 60 °C
194b 95% 10 h 60 °C 96% 48 h 60 °C
194c 95% 15 min 30 °C 95% 60 min 30 °C
248a 95% 20 min 30 °C 95% 45 min 30 °C
248b 97% 13 min 30 °C
248b). The corresponding methyl-substituted analogue,

which is supposed to be even more active, could not be
prepared thus far. The relevance of steric effects is further
emphasized by increasing the bulk on the substrate 246. For
example, the formation of the trisubstituted cyclopentene
product 247b has been slightly slower with the CAAC-
ruthenium complex (194c) than with the benchmark 248b;
yet, these first results clearly emphasize the potential of less-
stabilized carbene ligands in metathesis reactions.
imidazolylidene coordination has a distinct influence on such The observed differences in catalytic activity have been
a reaction pathway. attributed to the high sensitivity of the initiation step toward
steric modifications. Specifically, rotation about the
5.3. Olefin Metathesis RudCbenzylidene bond upon Ru-O bond dissociation is criti-
cally dependent upon the available space in close proximity
Cyclic (amino)(alkyl)carbene ruthenium complexes have to the aryl substituent at nitrogen. The opposite trends in
been exploited as olefin metathesis catalysts.136,171 The catalyst activity for 2-imidazolylidenes and cyclic (ami-
complexes 194, which feature different bulk at the carbene no)(alkyl) carbenes with bulkier substituents, viz., enhanced
ligand, can be used for ring-closing metathesis reactions and activity of 248 vs reduced performance of 194, is explainable,
are compared to the benchmark systems 248 (see Scheme in part, by the shorter Ru-Ccarbene bond in the CAAC
92 and Table 6). The catalytic activity at the Ru center is complexes. As a consequence, rotation about the N-Caryl
strongly dependent on the steric bulk imposed by the ligand. bond and about the Caryl-Calkyl bonds within the nitrogen
Complex 194a that contains a large cyclohexyl group substituent is also inhibited.
adjacent to the carbene moiety is the slowest catalyst and
requires heating to 60 °C. The activity of the dimethyl-
substituted carbene complex 194b is considerably higher and
6. Conclusions
has been further improved by reducing the bulk at the aryl For a long time, the transition-metal chemistry of less-
nitrogen substituent from diisopropylaryl to diethylaryl stabilized N-heterocyclic carbenes (NHCs) has been a rather
groups. Complex 194c displays ring-closing metathesis neglected area of study. Within the past few years, and
activity that is comparable to the most active precursor certainly stimulated by many serendipitous discoveries as
complexes featuring classical carbene ligands known (e.g., well as rational complex synthesis, the relevance of this type
Figure 11. Qualitative estimation of the donor strength of carbenes with reduced heteroatom stabilization, as compared to normal
2-imidazolylidenes and other carbene ligands (based on spectroscopy, reactivity, and calculations).
of carbene ligands has been emphasized. Various preparative (4) (a) Gruendemann, S.; Kovacevic, A.; Albrecht, M.; Faller, J. W.;
Crabtree, R. H. Chem. Commun. 2001, 2274. (b) Wanzlick, H.-W.;
routes are now available to make such compounds (cf. Table Schönherr, H.-J. Angew. Chem., Int. Ed. Engl. 1968, 7, 141. (c) Öfele,
1). Although some of these methods are probably rather K. J. Organomet. Chem. 1968, 12, P42. (d) Cardin, D. J.; Cetinkaya,
limited to certain complexes and thus difficult to extrapolate B.; Lappert, M. F.; Manojlovic-Muir, L.; Muir, K. W. Chem.
(for example, to include chelate formation or to install a Commun. 1971, 400.
(5) Arduengo, A. J.; Harlow, R. L.; Kline, M. J. Am. Chem. Soc. 1991,
variety of different metal centers), others are more widely 113, 361.
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Beyond Conventional N-Heterocyclic Carbenes: Abnormal, Remote, and Other Classes of NHC Ligands With Reduced Heteroatom Stabilization

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Beyond Conventional N-Heterocyclic Carbenes: Abnormal, Remote, and Other Classes of NHC Ligands With Reduced Heteroatom Stabilization

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Beyond Conventional N-Heterocyclic Carbenes: Abnormal, Remote, and Other Classes of NHC Ligands With Reduced Heteroatom Stabilization

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Chem. Rev.

2009, 109, 3445–3478 3445

Beyond Conventional N-Heterocyclic Carbenes: Abnormal, Remote, and Other

Received November 5, 2008

Contents 5.2. Hydrogenation and Hydrosilylation Reactions 3473

Martin Albrecht studied chemistry at the University of Bern (Switzerland)

theme are found via the replacement or displacement of one

C-H bond activation • 2-imidazolylidenes and related ligandsa

C-E bond activation • 2-imidazolylidenes (E ) CH3: activation with AgI; E ) CO2-:

C-X oxidative addition • 2-imidazolylidenes and related ligandsa

transmetallation • 2-imidazolylidenes (predominantly from Ag complexes)

heteroatom alkylation • 3-pyrazolylidenes

cycloaddition to Fischer carbenes • 2-imidazolylidenes and related ligandsa

A final preliminary remark concerns the controversial

multiple factors.18 Calculations suggest that C2 bonding and

2.1.2. C-H Bond Activation of C2-Substituted

Scheme 6 a Tolman electronic parameter (TEP)29 of ν ) 2039 cm-1

Scheme 9).32 Remarkably, the donor properties of these Scheme 10

Figure 3. Sterically identical palladium(II) complexes that are

ligand precursor 35.33 In the presence of NaOAc, smooth

Scheme 18 of the 1,4-disubstituted triazols 56 at the N3-position gives

2.3. Pyrazolylidene and Isothiazolylidene

Table 2. Spectroscopic Data for Rhodium Complexes

Oxidative addition was also successfully used for the

the overlapping orbitals at the carbene carbon is substantially

2.3.5. Cycloaddition to Fischer Carbene Complexes

Scheme 38 2-imidazolylidene complexes.77,78 Crystallographic analysis of

derived NHC complexes than in the corresponding 2-imi-

ridylidene complexes via the protonation or alkylation of Scheme 45

Figure 8. Proposed iridium structure 145, and the crystallographi-

site, providing an alternative approach toward the formation

Scheme 52 Crystallographic analysis shows a Pt-C bond distance of

Deuterium labeling experiments provide evidence that the

to be remarkably stable, despite the lack of a stabilizing

Scheme 64 complex decomposition. Although, apparently, steric bulk

2.5.4. Cycloaddition to Fischer Carbene Complexes

Figure 10. Representative examples of N-heterocyclic carbene

Representative products of these reactions are shown in

The six-membered analog of the heterocyclic carbene in

In NHC complex chemistry, the prevalence of metal-ligand Scheme 81

C3-bound pyrazolylidene 73 Mizoroki-Heck 57

C2-bound pyridylidene 156b, 232 Mizoroki-Heck 111

cyclic (amino)(alkyl)carbene 188a R-keto arylation 131

Scheme 83 However, it is a considerably more-active complex than

Scheme 85 nickel(0) form. A related C2-bound bis(2-imidazolylidene)

5.2. Hydrogenation and Hydrosilylation Reactions

Scheme 92 Table 6. Comparison of Catalytic Activities of Ru-Carbene

248b). The corresponding methyl-substituted analogue,

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