Construct the valence molecular orbital diagram for PL5.

Sigma bonding ligands contribute sp type

hybrid orbitals, which "look" very much like H 1sAOs (diagram to left), thus the diagram can be build up
using H-like AOs. hint: Prepare a lidand MO diagram from equatorial (H3) and axial (H2) fragments
(diagram to right). Then form the final MO diagram combining the L5 fragment with the P atom (No MO
mixing occurs).

P P x
y
equitorial
axial
 Forming a MO diagram
1. determine the molecular shape and identify the point group of the molecule
2. define the axial system find all of the symmetry operations on the molecule
3. identify the chemical fragments, and put them along the bottom of the diagram
4. determine the energy levels and symmetry labels of the fragment orbitals
5. combine fragment orbitals of the same symmetry, estimate the splitting energy and draw in the MO
energy levels and MOs (in pencil!)
6. determine the number of electrons in each fragment and hence the central MO region, add them to the
diagram
7. identify if any MO mixing occurs, determine the mixed orbitals and redraw the MO diagram with
shifted energy levels and the mixed MOs
8. use the MO diagram check-list!
9. analyse the MO diagram

shape has been given, point group is D3h

axial system has been defined, symmetry operations:
C3 S3
" v!
"v F
C2! F
"h
F F
F P F P
C2 F C2!! F
" v!!
F F

a1'

e e

a2" a2"

"isolated"
these orbitals can be a1' sigma orbital
determined by
analogy with the H3
orbitals covered in a1'
lectures, they lie
closer together than a1'
the axial orbitals and these orbitals are seperated
so interact more by 2 bonds and so will not
strongly interact strongly hence
there is only slight
stabilisation and
destabilisation

L! L!

L! L!
L! L!
L! L!

L! L!
MO diagram shown below
3a1'

a1'
2e' e'
non-bonding as a1'
we have already
used the a1' FO P 2a2"
on P

a1' a2"
2a1'
P is not particularly
electronegative so
I've placed the P
P P pz a2" pAOs slightly above
e' ligand non-bonding
sigma orbitals
a2"
(px, py) e'
P
"isolated"
sigma orbital
a1' given this FO energy
a1' alignment, the a2" and
e' orbitals are close in
P energy and overlap of
a2" the fragment orbitals is
expected to be large.
it is difficult to 1a2" Therefore the splitting
predict the
ordering of these energy is of both sets
two orbitals and of MOs is expected to
a calculation is 1e' be large.
required

e'

the splitting between

1a1'
these a1 MO is large note: orbital
becuase sFOs have the labeling ignores
strognest interactions L! core orbitals z
L!
and the energy of the L!
FOs is quite close L! L! x
L! L! P P L!
L! L! L! P
L!
L! 5e L! 10e 5e y
L!
mixing could conceivably occur between the 2a1' and 3a1' MOs because they are close in energy, one
orbital is non-bonding, and one orbital is occupied while the other is unoccupied. However, this is
unlikely to occur because the net interactions are destabilising as shown below (and actually these orbitals
contain the same equatorial fragment orbital component, and MOs with the same fragment components
do not mix)
highly antibonding

P +

2a1' 3a1' highly

antibonding

P +

-2a1' 3a1'