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NAMA : IKA CHASANATUN NIMAH

NIM : 24030116140090

KELAS : ANORGANIK C

HOMO-LUMO ("filled-empty") Orbital Interactions

A fundamental principle: all steps of all heterolytic reaction mechanisms are


either Bronsted or Lewis acid-base reactions

They involve either proton transfer (Bronsted), or unshared pair/empty


orbital interactions (Lewis).
When the interacting atomic orbitals are considered, the Bronsted reactions
can be seen as simply a special case of the Lewis, in which the empty
orbital is the antibonding orbital of the H-X bond.

In short, all heterolytic reactions are just examples of interactions between filled
atomic or molecular orbitals and empty atomic or molecular orbitals - that is,
Lewis acid-base reactions. Here is a diagram to explain this point:

The interaction of any two atomic or molecular orbitals, as you learned in general
chemistry, produces two new orbitals.
One of the new orbitals is higher in energy than the original ones (the
antibonding orbital), and one is lower (the bonding orbital).
When one of the initial orbitals is filled with a pair of electrons (a Lewis
base), and the other is empty (a Lewis acid), we can place the two electrons
into the lower energy of the two new orbitals.
The "filled-empty" interaction therefore is stabilizing.

When we are dealing with interacting molecular orbitals, the two that interact are
generally

The highest energy occupied molecular orbital (HOMO) of one molecule,


The lowest energy unoccupied molecular orbital (LUMO) of the other
molecule.
These orbitals are the pair that lie closest in energy of any pair of orbitals
in the two molecules, which allows them to interact most strongly.
These orbitals are sometimes called the frontier orbitals, because they lie
at the outermost boundaries of the electrons of the molecules.

Here is the filled-empty interaction redrawn as a HOMO-LUMO interaction.


Let's look at some examples. First, a reaction that you would have categorized as
a Lewis acid-base reaction when you were studying general chemistry:

NH3 has an unshared pair on nitrogen, occupying the HOMO (it is generally true
that unshared pairs occupy HOMOs). BH3 has an empty valence orbital on B,
since B is a Group II element. This is the LUMO.

Here are pictures of the two orbitals from AM1 semi-empirical molecular orbital
calculations:

NH3 HOMO BH3 LUMO

The HOMO-LUMO energy diagram above describes the formation of a bond


between N and B.

Now let's try a slightly more complex case. Here's a typical Bronsted acid-base
reaction:
The curly arrows track which bonds are made, and which are broken, but they do
not indicate what orbitals are involved.

Water is both a Bronsted base (capable of accepting a proton) and a Lewis


base, with one of its unshared pairs (the HOMO).
H-Cl is a Bronsted acid, capable of donating a proton, but it also is a Lewis
acid, using the s* orbital of the H-Cl bond (the LUMO).
Here are pictures of the relevant HOMO and LUMO, again from AM1
semi-empirical molecular orbital calculations:

H2O HOMO HCl LUMO

The interaction stabilizes the unshared pair of the oxygen, while


simultaneously breaking the H-Cl bond because the interaction is with the
antibonding orbital.
Another example is the SN2 reaction, which involves the HOMO of the
nucleophile and the s* orbital of the R-X bond:

Here are the relevant orbitals:

OH- HOMO CH3-Cl LUMO

The interaction stabilizes the unshared pair of the oxygen, while simultaneously
breaking the CH3-Cl bond because the interaction is with the antibonding orbital.

Other examples include the reaction of alkenes with H-X, where the HOMO is
the p MO of the alkene and the LUMO is the H-X s* orbital:
and the capture of the carobcation in an SN1 reaction by nucleophile:

You should need no reminder that the carbocation is stabilized by a filled-empty


interaction between the empty p orbital of the positive carbon and the s orbital of
an adjacent C-H or C-C bond
In short, all heterolytic reactions proceed because the energy of a pair of electrons
is lowered by the interaction of a filled atomic or molecular orbital with an empty
one.