3 center-2 electron Bond

Contents:

 Definition.
 Introduction.
 Diborane(Introduction).
 Structure and bonding.
 Explanation of 3c-2e by other examples.
 Transition metal complexes.
 Other compounds like Beryllium
and Carbocations.
 2-Norbornyl cation.
Definition:-

 In a 'three center two electron bond' the

two electrons are 'shared' by three separate
nuclei. This happens usually with elements that
can form electron deficient bonds. The simplest
example of this is Diborane (B2H6). As the
probability distribution of this bond is shaped as
a banana it is also known as a banana bond.
Introduction:-

 3-center 2-electron (3c–2e) bond is electron-

deficient chemical bond where three atoms
share two electrons.
 The combination of three atomic orbitals
form three molecular orbitals: one bonding,
one non-bonding, and one anti-bonding.
 The two electrons go into the bonding orbital,
resulting in a net bonding effect and
constituting a chemical bond among all three
atoms.
Introduction:-

 In many common bonds of this type, the

bonding orbital is shifted towards two of the
three atoms instead of being spread equally
among all three.
 An example of a 3c–2e bond is trihydrogen
cation H+3. This type of bond is also
called banana bond.
Diborane(Introduction):

 Diborane(6), generally known as diborane is

the chemical compound consisting
of boron and hydrogen with the formula B2H6.
 Diborane is a key boron compound with a
variety of applications. It has attracted wide
attention for its electronic structure. Its
derivatives are useful reagents.
Structure and bonding:

 Diborane is an electron-deficient molecule which does not

have enough valence electrons to form a separate two-
electron bond between each pair of bonded atoms.
 For the eight atoms of B2H6, this would require a minimum of
seven bonds and therefore fourteen valence electrons (as in
ethane, C2H6), but B2H6 has only twelve valence electrons.
 Instead diborane adopts a bridged structure of D2h symmetry
containing four terminal and two bridging hydrogen atoms.
 The model determined by molecular orbital theory indicates
that the bonds between boron and the terminal hydrogen
atoms are conventional 2-center, 2-electron covalent bonds.
Continue…
 The bonding between the boron atoms and the bridging hydrogen
atoms is, however, different from that in molecules such as
hydrocarbons.
 Each boron uses two electrons in bonding to the terminal hydrogen
atoms, and has one valence electron remaining for additional
bonding.
 The bridging hydrogen atoms provide one electron each.
 The B2H2 ring is held together by four electrons which form two 3-
center 2-electron bonds.
 This type of bond is sometimes called a 'banana bond'.
 The lengths of the B-Hbridge bonds and the B-Hterminal bonds are 1.33 and
1.19 Å respectively, and this difference in the lengths of these bonds
reflects the difference in their strengths, the B-H bridge bonds being
relatively weaker.
Continue…
 Bonding diagram of
diborane (B2H6) showing
with curved lines a pair
of three-center two-
electron bonds, each of
which consists of a pair
of electrons bonding
three atoms, two boron
atoms and a hydrogen
atom in the middle.
Explanation of 3c-2e by other
examples:-
 Boranes and carboranes:
 An extended version of the 3c–2e bond model
features heavily in cluster
compounds described by the polyhedral
skeletal electron pair theory, such
as boranes and carboranes. These molecules
derive their stability from having a
completely filled set of bonding molecular
orbitals as outlined by Wade's rules.
Continue…

 The monomer BH3 is unstable since the boron

atom has an empty p-orbital. A B−H−B 3-center-
2-electron bond is formed when a boron atom
shares electrons with a B−H bond on another
boron atom. The two electrons (corresponding to
one bond) in a B−H−B bonding molecular orbital
are spread out across three inter nuclear spaces.
Continue…

 In diborane(B2H6), there are two such 3c-2e

bonds:
 Two H atoms bridge the two B atoms, leaving
two additional H atoms in ordinary B−H bonds
on each B.
 As a result, the molecule achieves stability since
each B participates in a total of four bonds and
all bonding molecular orbitals are filled,
although two of the four bonds are 3-centre
B−H−B bonds.
Continue…

 The reported bond

order for each B−H
interaction in a bridge is
0.5, so that the bridging
B−H−B bonds are
weaker and longer than
the terminal B−H bonds,
as shown by the bond
lengths in the structural
diagram.
Transition metal complexes

 Three-center, two-electron bonding is pervasive

in organotransition metal chemistry. A celebrated
family of compounds featuring such interactions
as called agostic complexes.
 Agostic interaction is a term in organometallic
chemistry for the interaction of a coordinatively-
unsaturated transition metal with a C−H bond,
when the two electrons involved in the C−H bond
enter the empty d-orbital of a transition metal,
resulting in a three-center two-electron bond.
 Other compounds like Beryllium
and Carbocations

 Other compounds:
 This bonding pattern is also seen
in trimethylaluminium, which forms a dimer
Al2(CH3)6 with the carbon atoms of two of
the methyl groups in bridging positions.
 This type of bond also occurs in
carbon compounds, where it is sometimes
referred to as hyperconjugation; another name
for asymmetrical three-center two-electron
bonds.
Countine…

 One of
many transition
metal silane
complexes,
examples feature
three-center two-
electron bonding.
Beryllium:-

 The first stable subvalent Be complex ever

observed contains a three-center two-
electron π-bond that consists of donor-
acceptor interactions over the C-Be-C core of
a Be(0)-carbene adduct.
Carbocations:

 Carbocations rearrangement reactions occur through

three-center bond transition states. Because the
three center bond structures have about the same
energy as carbocations, there is generally virtually no
activation energy for these rearrangements so they
occur with extraordinarily high rates.
 Carbonium ions such as ethanium C2H+7have three-
center two-electron bonds.
 Perhaps the best known and studied structure of this
sort is the 2-Norbornyl cation.
2-Norbornyl cation
 The 2-norbornyl cation has been formed from a variety
of norbornane derivatives and reagents.
 First reports of its formation and reactivity published
by Saul Winstein sparked controversy over the nature
of its bonding, as he involed a three-center two-
electron bond to explain the stereoselectivity of the
resulting product.
 Herbert C. Brown challenged this assertion on the
grounds that classical resonance structures could
explain the stereospecificity without needing to adapt
a new perspective of bonding.
 The nature of bonding in the 2-norbornyl
cation incorporated many new ideas into the
field’s understanding of chemical bonds.
Similarities can be seen between this cation
and others, such as boranes.