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).

z
P P

x y
equitorial axial

 1. 2. 3. 4. 5. 6. 7. 8. 9.

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

shape has been given, point group is D3h axial system has been defined, symmetry operations: C3 S3

"v
C2
F

F P F F F

"v ! C2 !
"v !!
C2 !!
F

F P F F F

"h

a1'

e a2" a2" a1' "isolated" sigma orbital

these orbitals can be determined by analogy with the H3 orbitals covered in lectures, they lie closer together than the axial orbitals and so interact more strongly

a1' a1'

these orbitals are seperated by 2 bonds and so will not 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' non-bonding as we have already used the a1' FO on P a1'

P

e'

2a2"

a1' 2a1'

a2" P is not particularly electronegative so I've placed the P pAOs slightly above ligand non-bonding sigma orbitals

pz a2"

e' a2"
P

(px, py) e'

a1'
P

it is difficult to predict the ordering of these two orbitals and a calculation is required

1a2" 1e'

"isolated" sigma orbital given this FO energy a1' alignment, the a2" and e' orbitals are close in energy and overlap of the fragment orbitals is a2" expected to be large. Therefore the splitting energy is of both sets of MOs is expected to be large.

e'

the splitting between these a1 MO is large becuase sFOs have the strognest interactions and the energy of the FOs is quite close

1a1'
L! L! L! L! L! L! L! P L! L! L!

note: orbital labeling ignores core orbitals

P

z
L! L! P L! L!

5e

10e

5e

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

L!

2a1'

3a1'

highly antibonding

-2a1'

3a1'