Chemistry Reference
In-Depth Information
TABLE 4.1. Rate Constants and Selectivity Data for Reactions of Nitrenium Ions with
N
3
and Solvent
a
10
9
k
az
(M
1
s
1
)
k
s
(s
1
)
Ion
log S
0.02
b
64a
0.15
c
64b
3.4
10
4
5.07
d
64g
4.0
7.7
10
4
4.74
e
4.79
e
4.76
f
64h
4.2
6.3
10
6
3.10
g
64k
7.9
1.6
10
7
2.52
h
2.45
i
64l
5.3
0.88
j
64m
1.8
10
6
3.44
d
64n
5.0
2.7
10
6
3.55
k
3.46
l
9.6
5.9
10
6
2.94
e
3.00
l
64o
5.1
6.59
k
1.6
10
3
64p
6.1
2.7
10
5
4.53
k
64q
9.2
0.49
f
64r
0.04
f
64s
1.8
10
6
3.48
m
64t
5.4
1.1
10
6
3.68
m
64u
5.3
2.73
f
64v
2.2
10
2
7.25
n
64w
3.9
1.66
f
64x
4.15
f
a
Conditions: 5% CH
3
CN-H
2
O,
m¼
0.5 (NaClO
4
),
T¼
20
C, unless otherwise indicated. If
k
az
and
k
s
are
reported, the rate constants were directly measured from photochemically generated ions. If only log
S
is
reported, the selectivity was measured by the azide clock procedure.
S
is the observed [azide adduct]/
[hydration product] ratio extrapolated to 1M N
3
.
b
Ref. 107: H
2
Oat25
C,
m¼
1.0. This value is derived from Br
trapping, but it appears that
k
Br
k
az
.
c
Ref. 109: at 50
C.
d
Ref. 21.
e
Ref. 20.
1.1
10
6
o
64y
f
Ref. 109.
g
Ref. 28: 20% CH
3
CN-H
2
O,
m¼
0.0.
h
Ref. 28.
i
Ref. 27.
j
Ref. 106: H
2
Oat40
C,
m¼
1.0.
k
Ref. 23. 20% CH
3
CN-H
2
O,
m¼
0.0.
l
Ref. 19.
m
Ref. 113: H
2
O.
n
Ref. 114: H
2
O,
m¼
0.0.
o
Ref. 116.
