5.

04, Principles of Inorganic Chemistry II

MIT Department of Chemistry
Lecture 14: ML6 Sigma Complexes

The appropriate basis is

L1

L6 L5
M

L3 L4
x y
L2

As discussed previously,  bonds do not change phase along internuclear axis. Thus
orbital that move under R contribute O to the representation, orbitals that do not
move contribute +1.

Oh E 8C3 6C2 6C4 3C2 (=C42) i 6S4 8S4 3h 6d

 6 0 0 2 2 0 0 0 4 2

 = a1g + t1u + eg

Need now to determine the SALCs of the L set. Can do so by three different
methods… will demonstrate all of them.

Method 1

Projection operator method… projecting out L (a1g). Realize that complete ligand
mixing is preserved in O… thus will drop to pure rotational subgroup.

O E C3 C3 C3 C3 C3 C3 C3 C3 C2 C2 C2 C2 C2 C2 C4 C4 C4 C4 C4 C4 C2 C2 C2
L1
L1 L3 L4 L4 L5 L6 L5 L6 L3 L2 L2 L6 L5 L4 L3 L1 L1 L5 L3 L4 L6 L1 L2 L2

(

pa1 (L1 ) ~ 4 L1 + L 2 + L 3 + L 4 + L 5 + L 6)
1

a1g =
6
(L 1 + L2 + L3 + L4 + L5 +L )
6

5.04, Principles of Inorganic Chemistry II Lecture 14

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Method 2

A Schmidt orthogonalization can extract SALC’s from a non-symmetry adapted

linear combination of an appropriate basis. Suppose we have a SALC, v1, then there
exists a v2 that meets the following condition,

v2 =
v1 + μ
non symmetry adapted linear combination

multiplying by v1 gives,
0 1
v2v1 =
v 1v1 + μv1


= -μv1

To see how this works, lets consider the eg orbital basis. Using the Oh (O) character
table, may project out one of the SALC’s:

(1)
eg = 2L1 + 2L 2
L 3
L 4
L 5
L 6

But the other can not be obtained from the character table. Application of peg to L2
gives us
eg(1) back again. Application to L3 gives:

e 1
P g (L 3 ) =
12
(2L 3 + 2L 5
L1
L 2
L 4
L 6 )
This new wave function is not
eg(2) because it is not orthogonal to
eg(1)… so it must
be a linear combination of
eg(1) and
eg(2). Applying the above procedure:

 
1 1
a =
μv1 =
 2L 3 + 2L 5
L1
L 2
L 4
L 6 2L 1 + 2L 2
L 3
L 4
L 5
L 6 
 12 12 
1 1
=

12
[ ]

6 = +
2
so,
1 1 1
v 2 =
2 12
(
2L1 + 2L 2
L 3
L 4
L 5
L 6 +
12
) (
2L 3 + 2L 5
L1
L 2
L 4
L 6 )
1  3 3 3 3 
=  L 3 + L 5
 L 4 + L 6   L 3 + L 5
L 4 + L 6
12  2 2
2 2


( ) ( )

(2) 1
 eg = (L3
L4 + L5
L6 ) this is orthogonal to
eg(1)… thus
2
it is the other SALC.

5.04, Principles of Inorganic Chemistry II Lecture 14

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Method 3

May adapt the symmetry of the ligand set to the symmetry of the metal orbitals.

Consider dz2 (eg )

L1
L5
eg  2L1 + 2L 2
L 3
L 4
L 5
L 6
L6 L4 1
eg =
12
(2L 1 + 2L 2
L 3
L 4
L 5
L 6 )
L3
2z2-x2-y2
L2

Using any of the above methods, the following may be deduced:

1

a1g =
6
(L 1 + L2 + L3 + L4 + L5 + L6 )
L1
L5

L6 L4 S

L3
L2

(1) 1 (2) 1
eg =
12
(2L 1 + 2L 2
L 3
L 4
L 5
L 6 ) eg =
2
(
L3
L4 + L5
L6 )
L1
L5 L5

L6 L4 dz2 L6 L4 2
dx -dy
2

L3 L3
L2

(1) 1 (2) 1 (3) 1

 t1u =
2
(L 1
L2 )  t1u =
2
(L 3
L4 )  t1u =
2
(L 5
L6 )
L1

L4

pz px L5 L6 py

L3

L2

5.04, Principles of Inorganic Chemistry II Lecture 14

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 The t2g d orbital set (i.e. dxy, dxz, dyz) is of incorrect symmetry to bond with a L
ligand set… the  orbital is directed between the lobes… e.g. dyz

L1

L5

L6 L4

L3

L2 these point toward center of “clover leaf”

With above considerations of
EML and SML in mind… the MO diagram for M(L)6 is…
Co(NH3)63+ example
(1)
4pz-t1u
t1u
(2)
M-L
* 4px-t1u
(3)
3.7eV 4py-t1u

4p
Note: Interaction a1g
energies  and * M-L
* 4s-a1g
are usually smaller
than
EML…so
orbitals stay within
their “zones.” 4s
eg
M-L
*
7.3eV

because ao's composing

SALCs are at long distances
3d t2g (dxz, dyz, dxy) minimal overlap, so all
9.4 eV are degenerate
see pg cc 9

L
(1...6)
(1)
4pz-t1u
(2) ~10.8eV
4px-t1u see pg cc 9
(3)
4py-t1u
t1u
2 (1)
3dz +eg
2 2 (2)
eg 3dx -y +eg

a1g
M-L
4s+a1g

5.04, Principles of Inorganic Chemistry II Lecture 14

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