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pk

Bent Bond

Bent bond, also known as banana bond is a term in chemistry that refers to
a type of covalent chemical bond with geometry somewhat reminiscent of a banana.
The term itself is a general representation of electron density or configuration
resembling a similar "bent" structure within small ring molecules or as a
representation of double or triple bonds within a compound that is an alternative to
the sigma and pi bond model. Bent bond is formed by the oblique overlap of atomic
orbitals as a result of which the resultant bond bulges out in a circular fashion.

Bent bonds are a special type of chemical bonding in which the ordinary
hybridization state of two' atoms making up a chemical bond are modified with
increased or decreased s-orbital character in order to accommodate a particular
geometry. Bent bonds are found in strained organic compounds such as
cyclopropane, oxirane and aziridine. This bond model concept is used to explain the
structure of cyclic and substituted double bonds.

Fig.1a. Depiction of the banana bond in cyclopropane

Concept of Bent Bond

Bent bond is the model which is closely related to the subject of structures of
substituted double bonds. Such bond concept could be applied in two ways:

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1. The first relates to the ring strain of small cyclic molecules. Although
rehybridization occurs as ring size is decreased. e.g., in cyclopropane carbon
is sp3 hybridized. In such types of compounds, it is not possible for C-atoms
to assume the 109.5°bond angles with standard hybridization. Increasing the
p-character makes it possible to reduce to bond angles to 60°. At the same
time' the carbon to hydrogen bonds gain more a-character and shorten as
shown in Fig 1a & b.

Fig.1b. Depiction of the banana bond in cyclopropane

In cyclopropane the maximum electron density between two C-atoms does

not corresponds to the internuclear axis, hence the name bond bent. In
cyclopropane the interorbital angle is 104: This bonding can be observed
experimentally by X-rays diffraction of certain cyclopropane derivatives;
deformations density is outside the line of centers between carbons.

2. The second use of bent bonds is as an alternative interpretation of multiple

bonding. Multiple bonding can be explained by considering the example of
ethylene. In this molecule, the sigma bond is formed by head-on overlap of

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sp2-hybrid orbital of C-atoms and Pi bond is formed by the parallel overlap of

remaining p-orbitals on each of C-atoms.

Fig.2.Sigma and pi bonds formation in ethylene molecule

There are two methods for interpreting the bonding in multiple bonded
compounds. The first method of interpreting multiple bonds is the σ-π picture, which
was developed in the context of MOT. The second method has been advocated by
L. Pauling in VBT, but neither is limited to either MOT or VBT.

Fig.3. Sigma and pi bonds formation in ethylene molecule

The double bond in ethylene molecule consists of a sigma bond formed by the
head-on overlap of trigonal hybrids (sp2) on each C-atom and a π-bond is formed by
the sideways overlap of the remaining p-orbitals on each C-atom in Fig 3.

The orbitals will resemble the MOs (molecular orbitals). The two bonds are not
equivalent, since they differ in energy as well as symmetry. In accordance with the

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principle of maximum overlap, one should expect the sigma bond to be stronger than
the pi-bond. If we assume that the sigma bond in an ethylene molecule has the same
strength as that in ethane molecule, it would have the bond energy of about 347 kJ
mol-1. The experimental value of the bond dissociation energy of ethylene (breaking
sigma and pi bonds) is 598 kJ mol-1, indicating about 251 kJ mol-1 for the pi-bond.
The difference of some. 96 kJ mol-1 between the sigma and Pi bonds can be attributed
to the poor overlap of the latter.

According to Pauling approach the C-atom is considered to be hybridized

tetrahedrally (sp3 to the first approximation in all compounds, saturated or
unsaturated, multiple bonds are considered to be formed from the oblique overlap of
these hybrid orbital as shown in following Fig.4. The resulting bonds are called bent
bonds or banana bonds. Since the two bonds are equivalent, it is possible to assume
that each bent bond has an energy of 299 kJ mol-1.

Fig.4. Bent bond representation of ethylene molecule

Four Electrons Three Centre Bond

Generally there are two types of covalent bonds.

 First one is the ordinary two centre, two electron (2c - 2e) bond, formed
by the overlap of a p-orbital of the central atom with a a-orbital of an
outer atom,
 Second one is the three centre-four electron (3c -4e) bond, formed from
a p-orbital of the central atom and the a-orbital of two outer atoms. For

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example, three centre form electron (3c – 4e) bond model approach is
based on the two main ideas:

(i) Use of the outer d-orbitals of the central atom of non-

transition metal ion is so slight that these may be neglected
altogether.

(ii) Presence of bond angles close to 900 and 1800 in AB4

molecules suggests that orbitals perpendicular to one another are
being used.

For molecules with an octet, or less, of electrons in the valence shell of the
central atom, the hybridization employing sp, sp2 and sp3 orbitals remain valid. For·
example, Be atom in BeCl2 is sp hybridized, B in BF3 is sp2 hybridized and C in CH4
is sp3 hybridized. The 3c – 4e model has been proposed for molecules in which five
or more electron pairs on the central atom must be accounted for chemical bonding.
In molecules of AB4E type (SeF6, the central atom A is considered to use px and py
orbitals to bond the two B-atoms (F), while the remaining two B atoms (F) are bound
using pz orbital to form a 3c – 4e bond. The remaining electron pair on the central
atom is postulated to be occupying a pure s-orbital and have no stereo chemical role.
Similarly AB3E2 type (ClF3) molecule also has 3c – 4e bonding.

The MO theory explains the 3c - 4e bond as follows. The illustrate the idea, let us
take the example of XeF2, the valence shell configuration of Xe and F are X: 5s2 5p6,
and F: 2s2, 2p5. If the bonds lie in the x-direction, this 2px orbitals of each fluorine
bearing the unpaired electron and the filled 5px orbital of Xenon will participate in
forming three centre sigma MOS. Similarly, the 2py orbitals of fluorine along with
5py orbital of Xenon will form three-centre Pi-MOs. Thus, by using the pz orbitals
of the fluorine and Xenon we get another set of Pi-MOs. The corresponding πy and

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πz MOs are degenerate as usual. Here the Pi-system is of no interest from the stand
point of stability of the molecule, as the bonding, non-bonding and antibonding Pi-
MOs are completely filled in and yield the Pi-band order 'zero. (Fig 4).

Fig.4. The MO picture of XeF2 molecule

Bridge Bond and Electron Deficient Compounds

Bridge bond is a type of chemical bond in which one atom is linked between
the two atoms. There are some cases in which the number of available valence
electrons is not sufficient to display the normal electron pair bonds (2c - 2e) among
all the constituent atoms. In other words the molecules in which there are not enough
electrons to form covalent bonds between the atoms are called electron deficient
molecules. The occurrence of electron deficient covalent bonds is a common feature
of some elements of group 13 of the periodic table. For example (BH3)2, [Al(CH3)3]2
are electron deficient molecules. since they do not contain enough electrons to form
the two-electron bonds between the atoms.

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Ht Hb Ht
B1 B2
Ht Hb Ht

Fig 5a. Structure of Diborane

Diboranee (B2H6) is the best example to understand the bridge bond. Electron
diffraction studies have shown that B2H6 has a hydrogen bridged structure as shown
in Fig.5a & b in which two irregular BH3 tetrahedral have one edge in common,
Thus two boron atoms represented as B1 and B2 and four hydrogen atoms (called
terminal H-atoms and are represented as Ha-atoms) lie in the plane of the .paper
(coplanar) while the remaining two H-atoms (called bridging H-atom and hence
represented as Hb-atom) are located centrally above and below the plane of the paper.
These bridging H-atom prevent the notation between the two B-atoms. Specific heat
measurements also confirm that notation is hindered.

Fig 5b. Hydrogen bridge structure of B2H6

It is obvious that length of B1-Ht bond = B2-Ht bond which is equal to 119.A°,
This bond length is almost equal to that for a single bond given by the sum of the
single-bond normal covalent radii, of boron and hydrogen i.e., rB + rH which is equal
to 0.85 + 0.30 == 1.15A0 > rB + rH = 1.15A0 indicating the presence of fractional
bond.

Facts about the Bridge Structures

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Following facts support the bridge structure in diborane molecule.

1. 'Nuclear magnetic resonance (NMR) and Raman spectra have shown

that four hydrogen namely Ht-atom are of one type while the remaining
two namely Hb-atoms are of different types.

2. Specific heat measurements have shown that the two ends of the
molecule cannot be rotated against each other. This hindered notation
clearly indicates that the two bridging hydrogen' atoms lie in a plane at
right angles to that of boron atom and four terminal hydrogen atom.

3. The terminal and bridging position of the H-atoms has also been
confirmed by its chemical reactivity. When diborane is reacted with
methyl borane (BMe3), we get tetraethyl borane (CH3)4 B2H4 whose
structure is given as;

Fig 6. Tetramethyl borane

MO Theory and Bridge Bond

Bridge bond is also known as three-centre two electron (3c – 2e) bond. In
B2H6, each B-atom is sp3 hybridized. Among the four sp3 hybrid orbitals, one is
remaining vacant. Each boron utilizes two sp3 hybrid orbital to form two normal
electron pair (2c - 2e) terminal B - Ht bonds. Thus, the electron pair in each terminal
B - H, bond is localized between the nuclei in the bonding molecular orbital (2c –

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2e) formed through combination of Is-orbital of the terminal hydrogen and 2sp3
hybrid orbitals of the B-atom (Fig 7).

Fig 7. Three centers two electron bond (3c – 2e)

But for the bridging bonds, the three orbitals, i.e., one sp3 hybrid orbital from
each boron and Is orbital of the bridging H-atom, undergo LCAO to form three
centre molecular orbitals, i.e. bonding MO, nonbonding MO and antibonding MO.
The MO energy diagram for B2H6 is shown in Fig 8.

Fig. 8a. MO scheme for one of the B–H–B bridging three center two electron bonds
(This picture is still a simplification of the actual MO scheme)

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Fig. 8b. MO energy diagram of B2H6 molecule

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