Chemistry Reference
In-Depth Information
TABLE 6.4. Absorption Maxima for Aryl Nitrenium Ions Determined by LFP
Experiments and Calculations
Aryl Nitrenium Ion
Experimental (nm)
Theoretical (Singlet) (nm)
Method
500
450
TD-DFT
H
N
34
CASPT2
465
493
H
N
35
CASPT2
654
658
H
N
36
CASPT2
495
526
H
N
37
TD-DFT
486
441
H
Et
N
N
Et
O
2
N
38
TABLE 6.5. Effect of para Substitution on
D
E
st
of Phenyl
Nitrenium Ions Predicted by DFT (BPW91/cc-PVDZ)
Calculations
Nitrenium Ion
D
E
st
(kcal/mol)
27.8
H
3
C
H
N
N
H
3
C
39
26.7
H
H
3
C
O
N
40
21.9
H
CH
3
N
41
18.8
H
N
34
12.2
H
H
N
O
42
16.8
O
H
N
N
O
43
