Chemistry Reference
In-Depth Information
TABLE 9.8. Analysis of the Calculated D-Tensor (B3LYP/TZVPP) of o-6b
D
E
Total (calculated)
0.284
0.023
Experiment
0.357
0.014
Spin-spin
0.262
0.022
Spin-orbit
0.022
0.001
Spin-spin
1-Center
0.315
0.006
2-Center
0.047
0.034
3-Center
0.006
0.005
4-Center
0.000
0.000
Coulomb
0.172
0.025
Exchange
0.091
0.003
Spin-orbit
M¼
0(
a
!
a
)
0.006
0.003
M¼
0(
b!b
)
0.010
0.003
M¼þ
1(
b!
a
)
0.021
0.004
M¼
1(
a
!b
)
0.014
0.002
All values are given in units of cm
1
.
considerable contribution parallel to the
z
-direction of the nitrene dipolar field and
therefore to a smaller
E
-value of the quartet spin system compared to
p-
6b
. For
p-
6b,
the nitrene character in
o-
6b
still prevails over the carbene character, but unlike in
p-
and thus the easy axis of
the spin system can be shifted by the influence of the dipolar field of the carbene.
6b
there is no symmetry axis along the C
N bond in
o-
6b
FIGURE 9.17.
Orientation of the
D
-tensor of
o- 6b
based on the calculations B3LYP/TZVPP.
