Three-center two-electron bond

A three-center two-electron bond is an 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. 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. Examples of 3c-2e bonds
are the trihydrogen cation H+3 and the dimeric structure of aluminium chloride. This type of bond is also
called banana bond.

Banana bond
In organic chemistry, a bent bond, also known as a banana bond, is a type of covalent chemical bond with a
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, such as cyclopropane (C3H6) or
as a representation of double or triple bonds within a compound that is an alternative to the sigma and pi
bond model.

1. Diborane
Diborane adopts a D2h structure 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. The bonding between the boron atoms and the bridging
hydrogen atoms is, however, different from that in molecules such as hydrocarbons. Having used two electrons in
bonding to the terminal hydrogen atoms, each boron has one valence electron remaining for additional bonding.
The bridging hydrogen atoms provide one electron each. Thus the B2H2 ring is held together by four electrons,
an example of 3-center 2-electron bonding. This bond is 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-Hbridge bonds being relatively weaker.

Briefly saying, the structure of Diborane molecule consists of four hydrogen atoms and that of two boron atoms
coming on the same plane. In between these planes, there are said to be two dividing atoms of hydrogen. The
boron atom is known to be sp3 hybridized and has four hybrid orbitals. From these four hybrid orbitals, three of
the orbitals have one electron each, and of which one is an empty orbital. The two electrons of the hybrid orbitals
in each of the boron atoms form 2 bonds with the 1s hydrogen atoms. The two atoms of boron left with that of
each unpaired electron orbital and empty orbital forms the two bridging (B–H–B) bonds with that of the two 1s
hydrogen atoms, is also called as the banana bond.

2. Trimethyl Aluminium
Trimethylaluminium is one of the simplest examples of an organoaluminium compound. Despite its name it has
the formula Al2(CH3)6(abbreviated as Al2Me6 or TMA) as it exists as a dimer. This colourless liquid is an
industrially important compound but must be handled with care due to its pyrophoricity; it evolves white smoke
(aluminium oxides) when the vapour is released into the air.
AlMe exists mostly as a dimer at room temperature and pressure, analogous in structure and bonding to diborane.
As with diborane, the molecules are connected by 2 3-center-2-electron bonds: the shared methyl groups bridge
between the two aluminium atoms. The Al-C (terminal) and Al-C (bridging) distances are 1.97 and 2.14 Å,
respectively. The carbon atoms of the bridging methyl groups are each surrounded by five neighbors: three
hydrogen atoms and two aluminium atoms. The methyl groups interchange readily intramolecularly and
intermolecularly.
3-Centered-2-electron bonds are an example of "electron-deficient" molecules and tend to undergo reactions
with Lewis bases that would give products consisting of 2-centered-2-electron bonds. For example, upon
treatment with amines gives adducts RN-AlMe. Another reaction that gives products that follow the octet rule is
the reaction of AlMe with aluminium trichloride to give (AlMeCl).The monomer species AlMe, which has
an aluminium atom bonded to three methyl groups, occurs at high temperature and low pressure.[3]VSEPR
Theory predicts and electron diffraction confirms[5] that it has a trigonal planar (threefold) symmetry, as observed
in BMe.

3. Beryllium
The first stable subvalent Be complex ever observed contains a three-center two-electron bond π-bond that
consists of donor-acceptor interactions over the C-Be-C core of a Be(0)-carbene adduct.

4. Carbocations
Carbocation 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 C
2H+ 7 have three-center two-electron bonds. Perhaps the best known and studied structure of this sort is the 2-
Norbornyl cation.

Three centered four electron bonds

The 3-center 4-electron (3c–4e−) bond is a model used to explain bonding in certain hypervalent molecules such
as tetratomic and hexatomic interhalogen compounds, sulfur tetrafluoride, the xenon fluorides, and the bifluoride
ion.[1][2] It is also known as the Pimentel–Rundle three-center model after the work published by George C.
Pimentel in 1951,[3] which built on concepts developed earlier by Robert E. Rundle for electron-deficient
bonding.[4][5] An extended version of this model is used to describe the whole class of hypervalent molecules
such as phosphorus pentafluoride and sulfur hexafluoride as well as multi-center π-bonding such as ozone and
sulfur trioxide.
Examples of molecules exhibiting three-center four-electron bonding
σ 3c–4e−
 Triiodide
 Xenon difluoride
 Krypton difluoride
 Radon difluoride
 Argon fluorohydride
π 3c–4e−
 Carboxylates
 Amides
 Ozone
 Azide
 Allyl anion
Molecular orbital description

Figure 1: Diagram illustrating σ molecular orbitals of the triiodide anion.

The σ molecular orbitals (MOs) of triiodide can be constructed by considering the in-phase and out-of-phase
combinations of the central atom's p orbital (collinear with the bond axis) with the p orbitals of the peripheral
atoms. This exercise generates the diagram at right (Figure 1). Three molecular orbitals result from the
combination of the three relevant atomic orbitals, with the four electrons occupying the two MOs lowest in energy
– a bonding MO delocalized across all three centers, and a non-bonding MO localized on the peripheral centers.
Using this model, one sidesteps the need to invoke hypervalent bonding considerations at the central atom, since
the bonding orbital effectively consists of two 2-center-1-electron bonds (which together do not violate the octet
rule), and the other two electrons occupy the non-bonding orbital.

Valence bond (natural bond orbital) description

Figure 2: A donor-acceptor interaction diagram illustrating construction of the triiodide anion σ natural bond orbitals from
I2 and I−fragments.

In the natural bond orbital viewpoint of 3c–4e− bonding, the triiodide anion is constructed from the combination of
the diiodine (I2) σ molecular orbitals and an iodide (I−) lone pair. The I− lone pair acts as a 2-electron donor, while
the I2 σ* antibonding orbital acts as a 2-electron acceptor.[12] Combining the donor and acceptor in in-phase and
out-of-phase combinations results in the diagram depicted at right (Figure 2). Combining the donor lone pair with
the acceptor σ* antibonding orbital results in an overall lowering in energy of the highest-occupied orbital (ψ2).
While the diagram depicted in Figure 2 shows the right-hand atom as the donor, an equivalent diagram can be
constructed using the left-hand atom as the donor. This bonding scheme is succinctly summarized by the following
two resonance structures: I—I···I− ↔ I−···I—I (where "—" represents a single bond and "···" represents a weak
interaction with effective bond order of 0), which when averaged reproduces the I—I bond order of 0.5 obtained
both from natural bond orbital analysis and from molecular orbital theory.
Figure 3: Diagram depicting the natural bond orbital donor-acceptor interaction in neon difluoride. The central Ne atom acts
as the donor, while the out-of-phase combination of the peripheral F atoms acts as the acceptor. The two orbitals have been
overlaid on the same molecule framework.

More recent theoretical investigations suggest the existence of a novel type of donor-acceptor interaction that may
dominate in triatomic species with so-called "inverted electronegativity"[13]; that is, a situation in which the central
atom is more electronegative than the peripheral atoms. Molecules of theoretical curiosity such as neon difluoride
(NeF2) and berylium dilithide (BeLi2) represent examples of inverted electronegativity.[13] As a result of unusual
bonding situation, the donor lone pair ends up with significant electron density on the central atom, while the
acceptor is the "out-of-phase" combination of the p orbitals on the peripheral atoms. This bonding scheme is
depicted in Figure 3 for the theoretical noble gas dihalide NeF2.