Chemistry Reference
In-Depth Information
N
N
F
F
F
F
F
F
F
F
10
SCHEME 9.11.
Possible rearrangement to form
10
.
FIGURE 9.6.
Spin density distribution of azirinyl radical
10
(UB3LYP/6-311G(
d
,
p
)).
10
shows C
2v
symmetry, the spin density is delocalized into the aromatic
p
system.
has C
2v
symme-
try, and the spin density is delocalized into the aromatic system (Fig. 9.6). With a spin
population at the nitrogen atom of 0.6 but only 0.02 at the adjacent carbon atoms the
nitrogen atom bears the major part of the spin density.
Upon annealing of the matrix the iodine atom recombines with
o-
Quantum chemical calculations show that the azirinyl radical
10
6b
, observable
9b
0
increase
slightly under these conditions. The changes in intensity are very small, though.
by a decrease of its IR bands, but only the absorptions of ketenimine
o-
9.5 MATRIX ISOLATION AND SPECTROSCOPIC
CHARACTERIZATION OF NITRENO RADICALS
9.5.1 Phenyl Nitrene-4-yl
To synthesize the nitreno radicals
p-
6
in argon matrices, the corresponding azides
p-
7
have to be irradiated with UV light (254 nm, Scheme 9.12). Under these
