Chemistry Reference
In-Depth Information
FIGURE 5.6.
Energy diagram for the azido cleavage and nitrene formation of alkyl azides
35
and
58
. The numbers in parenthesis are the calculated (B3LYP/6-31
þ
G(
d
)) energies in
kilocalories per mole.
Source
: Reprinted with permission from the American Chemical
Society, Ref. 77.
H
H
O
O
O
h
ν
- N
2
.
Ph
.
N
3
N
N
3
.
N
Ph
.
Ph
Ph
H
62 63 64
65
SCHEME 5.26.
l
max
at
s. Muthukrishnan et al. used density-functional theory
calculations to support the proposed mechanism for the formation of the 1,5-ketyl
iminyl radicals. Thus, intramolecular H-atom abstraction in azidoalkanes is an
efficient method to form imine radicals.
300 nm and
t
¼
15
m
5.6 CONCLUSIONS
Triplet alkyl nitrenes can be formed by both intramolecular and intermolecular
triplet sensitization in both solution and the solid-state. Their reactivity is best
described as dimerization with other nitrenes or by reacting with another radical.
Even though triplet alkyl nitrenes react with molecular oxygen, the rate is low, and
