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5.04 Principles of Inorganic Chemistry II

Fall 2008

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5.04, Principles of Inorganic Chemistry II Prof. Daniel G. Nocera Lecture 13: Octahedral ML6 Complexes The basis set needs to be expanded for metal complexes with ligands containing orbitals. An appropriate basis for ligands with two orthogonal orbitals, e.g. CO, CN, O2, X, to the bond is shown below,

The arrow is indicative of the directional phase of the p orbitals. Owing to their ungerade symmetry, in constructing the p representation a p orbital, i.e. arrow, that transforms into itself contributes +1 a p orbital that transforms into minus itself contributes 1 a p orbital that moves, contributes 0 Oh E 6 12 8C3 0 0 6C2 0 0 6C4 2 0 3C2 2 4 i 0 0 6S4 0 0 8S6 0 0 3h 4 0 6d 2 0 a1g + t1u + eg t1g + t1u + t2g + t2u

There is a second method to derive the p basis. The Cartesian coordinate systems on each ligand contains the and basis sets. Thus the x,y,z irreducible representation (which is the sum of x + y + z or z + x,y for irreducible representations for which x,y,z are not triply degenerate) defines the 1 and 2p bonds of each ligand. Since the bond is coincident with the ligand, an unmoved atom is approximated by . On the basis of geometrical considerations, the following is true,
unmoved =

atoms

+ = x,y,z = +

5.04, Principles of Inorganic Chemistry II Prof. Daniel G. Nocera

Lecture 13 Page 1 of 4

Oh T1u = x,y,z

E 6 3

8C3 6C2 6C4 3C2 0 0 0 0 1 0 2 1 2 2 1 2

i 0 3 0

6S4 0 1 0

8S6 3h 6d 0 0 0 4 1 4 2 a1g + t1u + eg 1 a + eg + t1g + 2 1g 2t1u + t2g + t2u

+ 18

+ = a1g + eg + t1g+ 2t1u + t2g + t2u = a1g + t1u + eg = + = t1g + t1u + t2g + t2u The SALCs have already been derived in Lecture 12. Methods 1-3 of Lecture 12 can be employed to determine the p SALCs. For the orbitals that transform as t1u and t2g, Method 3 (mirror the metal atomic orbital symmetry) is convenient. For the t1u SALC, and 2 others (in the xz and yz planes as defined by the symmetries of the py and px orbitals) pz
(1 t1u) =

1 L 3 + L 4 + L 5 + L 6 2

The t2g SALCs have the mirrored symmetry of the (dxy,dxz,dyz) orbital set,

and 2 others (in the xy and xz planes as defined by the symmetries of the dxy and dxz orbitals)
1 L 1 L 2 L 4 + L 6 2

dyz

(1 t2g) =

Non-bonding SALCs must be ascertained from projection operators and Schmidt orthogonalization methods.

5.04, Principles of Inorganic Chemistry II Prof. Daniel G. Nocera

Lecture 13 Page 2 of 4

For a donor complex such as CoF63,

t1u

ML and ML

3.7 eV 4p see VOIE

a1g

ML note, the energy gap is small enough that this molecule is high spin ML ML (dx2y2, dz2) (dxz, dyz, dxy) decreased energy gap (relative to -only case) owing to participation of t2g orbitals in M-L antibond

7.3 eV 4s see VOIE

eg

9.4 eV 3d see VOIE

t2g

n.b t1g, t2u (M-L ) t1u (M-L ) t2g ML formed from pz, the s orbital on F too low in energy to participate in M-L bonding (VOIE = 40 eV) Co3+
t1u eg a1g CoF 63
6 F 6L

12L

F p orbitals, these are all degenerate at ~18.6 eV see VOIE of F, offset to reduce congestion arising from 18 orbitals at the same energy

5.04, Principles of Inorganic Chemistry II Prof. Daniel G. Nocera

Lecture 13 Page 3 of 4

For a -accepting ligand set, orbitals have the same form (or symmetry) as donors,

1
* * * * (1)
t1u =
L

3 +
L
4 +
L
5 +
L
6


2

t1u

1
* * * * (1)
t2g =
L

1 L
2 L
4 +
L
6


2

t2g

The only difference between the -donor and -acceptor MO diagrams is the relative placement of the * orbitals relative to the metal atomic orbitals; for Co(CN)63,
t1u ML and ML

3.7 eV 4p see VOIE ML a1g 7.3 eV 4s see VOIE

(M-L *) t2g

n.b t1g, t2u (M-L ) t1u eg ML

12L *

(dx2y2, dz2) increased energy gap (relative to -only case) owing to participation of t2g orbitals in M-L bond

9.4 eV 3d see VOIE ML (dxz, dyz, dxy) t2g 6L

the lone pair HOMO of CO, PES spectrum sets the energies of these orbitals at 14 eV

t1u ML eg a1g Co3+ Co(CN)63 6 CN

5.04, Principles of Inorganic Chemistry II Prof. Daniel G. Nocera

Lecture 13 Page 4 of 4