vibrational spectrum, (1) the adiabatic connection scheme (ACS) and (2) the decomposition of each normal mode into local mode contributions, which will be discussed
in the following section for [Ni(CO) 3 F]
À , the complex with the largest coupling error
of 100 cm
À1 . Figure 6a shows how the three equivalent local vibrational CO modes
ω
a (5,6,7) of [Ni(CO) 3 F]
À are transformed into the A 1 normal mode ω 18 , i.e., the TEP
N
F
H
H
N
H
H
H
P
H
H
H
As
H
H
H
N
OMe
OMe
OMe
P
OMe
OMe
OMe
As
OMe
OMe
OMe
Sb
OMe
OMe
OMe
Bi
OMe
OMe
OMe
N
F
F
H
N
I
I
I
N
At
At
At
N
F
F
F
N
Cl
Cl
Cl
N
Br
Br
Br
N
H
H
Cl
N
Cl
Cl
H
N
CF 3
Me
Me
N
Et
Et
Et
N
H
Me
Me
N
Me
Me
Me
N
Ph
Ph
Ph
N
H
H
Me
N
C 6 F 5
C 6 F 5
C 6 F 5
N
NH 2
NH 2
NH 2
N
NMe 2
NMe 2
NMe 2
P
I
I
I
P
At
At
At
P
H
H
F
P
F
F
H
P
F
F
F
P
Cl
Cl
Cl
P
Br
Br
Br
P
H
H
Cl
P
Cl
Cl
H
P
CF 3
Me
Me
P
H
Me
Me
P
Me
Me
Me
P
Ph
Ph
Ph
P
C 6 F 5
C 6 F 5
C 6 F 5
P
H
H
Me
P
Et
Et
Et
P
NH 2
NH 2
NH 2
P
NMe 2
NMe 2
NMe 2
As
H
H
F
As
F
F
H
As
F
F
F
As
Cl
Cl
Cl
As
Br
Br
Br
As
I
I
I
As
At
At
At
As
H
H
Cl
As
Cl
Cl
H
As
CF 3
Me
Me
As
H
Me
Me
As
Me
Me
Me
As
Ph
Ph
Ph
As
H
H
Me
As
Et
Et
Et
As
C 6 F 5
C 6 F 5
C 6 F 5
As
NH 2
NH 2
NH 2
As
NMe 2
NMe 2
NMe 2
Bi
H
H
H
Bi
H
H
F
Bi
F
F
H
Bi
F
F
F
Bi
Cl
Cl
Cl
Bi
Br
Br
Br
Bi
I
I
I
Bi
At
At
At
Bi
H
H
Cl
Bi
Cl
Cl
H
Sb
H
H
H
Sb
H
H
F
Sb
F
F
H
Sb
F
F
F
Sb
Cl
Cl
Cl
Sb
Br
Br
Br
Sb
I
I
I
Sb
At
At
At
Sb
H
H
Cl
Sb
Cl
Cl
H
Sb
CF 3
Me
Me
Sb
H
Me
Me
Sb
Me
Me
Me
Sb
Ph
Ph
Ph
Sb
H
H
Me
Sb
Et
Et
Et
Sb
C 6 F 5
C 6 F 5
C 6 F 5
Sb
NH 2
NH 2
NH 2
Sb
NMe 2
NMe 2
NMe 2
Bi
H
H
Me
Bi
Et
Et
Et
Bi
C 6 F 5
C 6 F 5
C 6 F 5
Bi
NH 2
NH 2
NH 2
Bi
NMe 2
NMe 2
NMe 2
Bi
CF 3
Me
Me
Bi
H
Me
Me
Bi
Me
Me
Me
Bi
Ph
Ph
Ph
Fig. 3 Schematic representation of the 181 ligands of [Ni(CO) 3 L] complexes investigated by
Setiawan and co-workers [274]: part 1. Reproduced from Ref. [274] with permission of the
American Chemical Society
242
E. Kraka and M. Freindorf