Professional Documents
Culture Documents
The basis set needs to be expanded for metal complexes with ligands containing
orbitals. Let’s consider ligands with two orthogonal orbitals, e.g. CO, CN-, O2-, X-,
to the bond:
L1
L5
L3
L2
The arrow is indicative of a directional phase of the p orbitals. Owing to their ungerade
symmetry:
( )
unmoved =
atoms
x,y,z = +
We will derive the orbitals pictorially (mirror metal ao symmetry)… other methods
may also be applied.
1
2
(
3 + 4 + 5 + 6 ) ± pz
7.3 eV 4s
eg (ML*)
decreased energy gap (relative to
-only case) owing to participation
t2g (ML*) of t2g orbitals as m-L antibond
2 2 2
3dz , 3dx -y
9.4 eV
3dxy, 3dxz, 3dyz
t1g
formed from px
t2g
n.b. t1g, t2u 12L and py orbitals
t1u
(VOIE = -19 eV)
t2u
(ML) t1u
(ML) t2g
a1g
6L eg formed from pz (VOIE
t1u t1u = 19 eV) the s orbital
on F too low in energy to
(ML) eg
participate in M-L bonding
a1g (VOIE = 40eV)
t1u t2g
1 * 1 *
2
(
3 + *4 + *5 + *6 ) 2
(
1 + *4 *2 *6 )
… the only difference is the relative placement of the * orbitals to the metal ao’s:
px, py, pz
(ML) t2g
a1g (ML*) t1g
t
(n.b.) t2u, t1g 12L 2g from L*, p , p
t1u x y
s t2u
t1u
(ML*, ML)
eg (ML*)
2 2 2
dx -y , dz
dxy, dxz, dyz
t2g (ML)
t1u
6Lp eg from L lp, pz
t1u a1g
ML eg
a1g