Boranes

Boranes
Polyhedral Boranes
An Important Class of Electron-Decient Borane Compounds
Hydroborane Clusters
1 Electron-deficient species possess fewer valence electrons than are required for a localized bonding
scheme
2 In a cluster atoms form a cage-like structure
3 There are a great number of known neutral and anionic hydroborane clusters
The Simplest Hydroborane B2H6
Hydride bridge bond , or three-center, twoelectron bond.
Normal covalent bond formed by overlap

of sp3 hybrid orbital from B with s orbital
from H.
H
H
H
B
B
H
H
H
Diborane
Instead of using pure AOs the SALCs for this MO
diagram are two sp3 hybrids from each B and the two
1s AOs for the bridging H atoms.
IUPAC Nomenclature of Boranes

The number of boron atoms is denoted by a prefix and the number of hydrogen atoms is given in
parentheses in the end.
For example: B2H6 is diborane(6), B5H11 is pentaborane(11)
Examples of Polyhedral Boranes
Polyboranes
The pyrolysis of B2H6 produces a variety of clusters and evolves
H2 gas. Once formed, many of these polyboranes are stable
compounds and many other elements can be placed into the
skeleton of borane clusters including carbon, other main group
elements and transition metals.
Naming Polyhedral Boranes

Closo; Nido; Arachno:::
Classification of structural types can often be done more

conveniently on the basis of valence electron counts.
Most classification schemes are based on a set of rules
formulated by Prof. Kenneth Wade, in 1971.
Families of Polyhedral Boranes
Wade's Rules and Classification Scheme For Polyhedral Borane Clusters

In a closo polyhedral borane structure:
The number of pairs of framework bonding electrons isdetermined by subtracting one B-H bonding
pair per boron.
The n+1 remaining framework electron pairs may be used inboron-boron bonding or in bonds
between boron and otherhydrogen atoms.
Example:
Tabular Summary of Wade's Rules Classification and Electron Count of Boron Hydrides
Closo comes from the Greek for cage, Nido the Latin for nest, Arachno the Greek for spider, Hypho the
Greek for net, and Klado the Greek for branch.
Heteroboranes
Many derivatives of boranes containing other main group atoms are also known.
These heteroboranes may be classied by formally converting the heteroatom to a BHx group having the
same number of valence electrons.
These represent the most common main group
heteroatoms incorporated into hydroborane
clusters.
Reactions of boranes and borohydrides
Heteroboranes
The preparation of one such cluster will serve to illustrate the general principles. First nido-B10H14
is activated by reaction with the Lewis base SEt2, which displaces bridging hydrogens to form
arachno-B10H12(SEt2)2. This reactive cluster adds one equivalent of acetylene to form1,2-closo[B10C2H12], which is now a neutral molecule. Heating of this compound in the absence of oxygen
forms at about 500C the re-arranged isomer 1,7-closo-[B10C2H12], and further heating to an
astounding 700C further isomerizes the structure to the 1,12-closo-[B10C2H12] isomer. Survival
of molecules at such extreme temperatures is an indication of remarkable and unusual chemical
stability. Structures are shown below
One of the most interesting applications of these carboranes is a result, oddly enough, of
converting them back to anionic structures. Thus 1,2-closo-[B10C2H12], despite its high thermal
stability, can be partially fragmented by a combination of the strong bases ethoxide and sodium
hydride. The deprotonated compound has the formula Na2[B9C2H11]. The structure of this
compound is shown below in a view that emphasizes the empty orbitals along the rim of five
boron and carbon atoms. It is isolobal to the extremely important cyclopentadienide anion,
perhaps the single most important ligand for organometallic complexes of the metals, being
used with transition, main-group, and f-elements. The carbollide anion, [B9C2H11]2, is a
dianion, and for certain metal ions, it forms stronger bonds than the mono-anionic [C5H5] is
capable of.
Even small-ring carbon-boron anionic rings can act as powerful donor ligands to transition
metals. For example the highly negative [B3C2H5]4 ring has a high tendency to form
multidecker sandwich complexes with late transition metals such as cobalt and nickel. The
structure of the ring, and two mixed-sandwich complexes of metals are shown. The
hydrocarbon [C5H5] of lower charge must be placed at the outsides of the sandwich, else the
charge cannot be fully compensated. But in the central layers, the carborane ring readily bonds
to two electron deficient metal ions.
2006
Douglas
Stephan
Douglas W. Stephan discovers the first example of a frustrated Lewis acid

base pair based on boron and phosphorus. Due to their unquenched reactivity
such molecules are able to heterolytically cleave dihydrogen molecule making
them potential metal free hydrogenation catalysts.
Synthesis of Poly(4-dibromoborylstyrene) (PS-BBr)
- A Well-Defined Soluble Polymeric Lewis Acids n
n BBr3
- n Me3SiBr
SiMe3
Br
PS-Si
Poly(4-dibromoborylstyrene) :
Br
PS-B
Model Compound :
PS-Si:
(29Si) = -4.4
4-isoPrPhSiMe3:
(29Si) = -4.4
PS-B:
(11B) = 54
4-isoPrPhBBr2:
(11B) = 55.8
(w1/2 = 2,500 Hz)
(w1/2 = 300 Hz)
Y. Qin, G. Cheng, A. Sundararaman, and F. Jkle J. Am. Chem. Soc. 2002, 124, 12672.
PS-BBr as Precursor to Other Organoboron Polymers
n
n
exc. Me3SiOEt
B
CH3CH2O
Br
OCH2CH3
exc. THF
OH
B
O
Br
PS-BBr2
PS-BOEt
HO
PS-BPin
BrCH2CH2CH2CH2O
SnMe3
B
O
B
OCH2CH2CH2CH2Br
PS-BOBu
PS-BTh
Increase in Lewis Acidity

Qin, Y.; Cheng, G.; Parab, K.; Obianuju, A., and Jkle, F. Macromolecules 2004, 37, 7123-7131.
For polymer modification reactions with a different poly(organoboron halide) see:
Chujo, Y.; Takizawa, N.; Sakurai, T. J. Chem. Soc., Chem. Commun. 1994, 227.
PS-BPF : A Polymeric Analog of B(C6F5)3
n
2 CuC6F5
F
B
Br
Br
F F
F
F
PS-BPF
19F
NMR Spectrum of PS-BPf
Compare with 4-isoPrPhB(C6F5)2 :
(19F) = -130.3 ; -149.1 ; -161.2
Y. Qin, G. Cheng, A. Sundararaman, and F. Jkle J. Am. Chem. Soc. 2002, 124, 12672.
PS-BPf : Lewis Acidity Determination
n
O
F
F F
F
F
PS-BPf
Lowering of
F
F
F
Fp
Fo
Fm
(19F) upon complexation
PS-BPf :
(19F) = 13.1
PS-BPf (aldehyde)n:
(19F) = 6.4
Downfield shift of 1H and 13C NMR signals of

coordinated crotonaldehyde
Lewis Acid
Relative
Acidity
BBr3
1.00
B(C6F5)3
0.72
PS-BPf
0.60
Estimation of Lewis acidity: R. F. Childs, D. L. Mulholland Can. J. Chem. 1982, 60, 801.
Lewis Acidic Boron Polymers in Materials Chemistry
Device Materials
O
Chemosensors
N
Al
O
Reversible Polymer
Assembly
AlQ3
+ 3n
-system
Tang , VanSlyke
-system
Luminescent polymer
Assembly
D
-D
n
N
B
O
Ar
n
-system
-system
Solution - Processable
Polymeric Materials?
Luminescence quenched

Boranes

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Boranes

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Boranes

Normal covalent bond formed by overlap

IUPAC Nomenclature of Boranes

Examples of Polyhedral Boranes

Naming Polyhedral Boranes

Classification of structural types can often be done more

Families of Polyhedral Boranes

Wade's Rules and Classification Scheme For Polyhedral Borane Clusters

Reactions of boranes and borohydrides

Douglas W. Stephan discovers the first example of a frustrated Lewis acid

Synthesis of Poly(4-dibromoborylstyrene) (PS-BBr)

- A Well-Defined Soluble Polymeric Lewis Acids n

(w1/2 = 2,500 Hz)

(w1/2 = 300 Hz)

PS-BBr as Precursor to Other Organoboron Polymers

Increase in Lewis Acidity

PS-BPF : A Polymeric Analog of B(C6F5)3

NMR Spectrum of PS-BPf

Compare with 4-isoPrPhB(C6F5)2 :

(19F) = -130.3 ; -149.1 ; -161.2

PS-BPf : Lewis Acidity Determination

(19F) upon complexation

Downfield shift of 1H and 13C NMR signals of

Lewis Acidic Boron Polymers in Materials Chemistry

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