5.

04, Principles of Inorganic Chemistry II

MIT Department of Chemistry
Lecture 12: Frontier Molecular Orbitals…
- Ligands

Metal complexes are Lewis acid-base adducts formed between metal ions and
ligands.

L
L ligand...Lewis base

L L

L
metal ion...Lewis acid
L

The interaction of the frontier atomic (for single atom ligands) or molecular (1, 2
atom ligands) orbitals of the ligand and metal lead to bond formation

*

y L
* y L
* interactions

m

nd, (n+1)s, (n+1)p x L
x L
interactions

z L z L interactions

 3 different ligand types:

-only,
-donor,
-acceptor

Before we tackle the business of the complex.... will need to consider the nature of
the ligand frontier orbitals.

5.04, Principles of Inorganic Chemistry II Lecture 12

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-donor: these ligands donate 2 e-s from an orbital of -symmetry

H- (1s2), NH3 (2a1 lp), PR3 (2a1 lp), CH3- (2a1 lp), OH2 (b1 lp)

analyzing this

LCAO
3 H (1s) + N

NH3
2s, 2px, 2py, 2pz

H orbitals can only form  bonds, therefore will choose 3  N-H bonds as our basis
set,

3
N
1
H
2 H
H

v"

v

v'

Transformation properties of the  bonds (in C3v symmetry) are as follows:

           
 1  1  1  2  1  1
E  2 
 2  C3  2 
 3   v 2 
 3 
           
 3  3  3  1  3  2

1 0 0 0 1 0 1 0 0
     
0 1 0 0 0 1 0 0 1
0 0 1 1 0 0 0 1 0
     
E C3 v

C3v E 2C3 3v

 3 0 1
a1 + e

5.04, Principles of Inorganic Chemistry II Lecture 12

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Projecting out the a1 and e SALCs of the 3H orbitals, we realize that the
transformation properties of the H orbitals are preserved in the C3 rotational
subgroup,

C3v E C3 C32 v v’ v”

1
1 2 3 1 3 2
this mixing is a
repeat of

dropping to C3

C3 E C3 C32
1
1 2 3

projecting out:

pa1 (1 )
1  E1 + 1  C31 + 1  C3 1 = 1 +  2 +  3

2

pe(1)(1 )
1  E1 + (*)C31 + C3 1 = 1 +  *  2 +  3

2

pe(2)(1 )
1  E1 + C31 + (*)C3 1 = 1 +  2 +  *  3

Taking appropriate linear combinations and normalizing:

a1 (L) = (1 +  2 +  3 )

3

1
e(+)(L) = (21
 2
 3 )

1
e(
)(L) = ( 2
 3 )

5.04, Principles of Inorganic Chemistry II Lecture 12

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Taking the LCAO: 3H SALCs (a1, e) + N(2s, 2px, 2py, 2pz)

2pz
±

2s
a1

b

a1 (see C3v character table)

LCAO
± 2py

(+)

e
LCAO
± 2px

b

z

y
x

Figure removed due to copyright considerations.

2e

2py 3a1

2px here is
lp used

e
for bonding to metal
2pz a1

2a1

(+)
e = ey
(-)
e = ex
a1
1e
2s a1

1a1

5.04, Principles of Inorganic Chemistry II Lecture 12

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 Why is one lone pair only available for bonding to metals?

z
y

1 O
2
H H x

2H SALCs: C2v E C2 v(xz) v(yz)

 2 0 2 0
a1 + b1
1
1 2 1 2  
s1pz px

1 2 1 2
1
pa1 (1 )  1  E1 + 1  C21 + 1  (xz)1 + 1  (yz)  1  a1 =
2
(
1 + 2 )
1
pb (1 )  1  E1 + (
1)  C21 + 1  (xz)1 + (
1)  (yz)  1  b =
2
(
1
2 )

3a1 s*

2b1 x*

b2
b1 b2 (HOMO) n.b.(
y)
a1

b1
a1
1b1 (x)

2a1 (z)
a1
this lp too low in
energy to
1a1 (s) participate in M-L
bonding
O 2H
H2O

5.04, Principles of Inorganic Chemistry II Lecture 12

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