Chemistry Reference
In-Depth Information
Table 1 Bond topological properties at the BCP of the formal S1
¼
N2 double bond in 1a,R
¼
Me
-
2
d
r
dð
N
Þ
d ðÞ
d
ðÞ
d
S
l
jj
l
3
r
r
1
l
2
l
3
e
ðÞ
B3PW91
6-31G(d)
1.55 1.76 8.36
10.01
7.14
25.52 0.40 0.96
0.60
1.61
0.39
6-31G(d,p)
1.55 1.76 8.33
10.02
7.14
25.50 0.40 0.96
0.60
1.61
0.39
6-31G(2d,p)
1.54 1.83
5.22
11.25
8.27
14.30 0.36 0.92
0.62
1.48
0.79
6-31G(3d,p)
1.53 1.86 1.46
11.65
8.57
21.68 0.36 0.92
0.61
1.52
0.54
6-31+G(d)
1.55 1.76 8.02
10.01
7.15
25.18 0.40 0.96
0.60
1.60
0.40
6-31+G(d,p)
1.55 1.76 7.89
10.00
7.15
25.04 0.40 0.96
0.60
1.60
0.40
6-311G(d,p)
1.54 1.80 6.14
10.31
7.51
23.96 0.37 0.95
0.60
1.58
0.43
6-311G(2d,p) 1.53 1.86
6.68
11.45
8.44
13.21 0.36 0.91
0.63
1.46
0.87
6-311G(3d,p) 1.53 1.87 0.45
11.70
8.61
20.76 0.36 0.92
0.61
1.50
0.56
cc-pVDZ
1.56 1.67 9.25
8.85
6.46
24.58 0.37 0.96
0.60
1.60
0.36
cc-pVTZ
1.54 1.86 3.65
11.02
7.77
22.43 0.42 0.94
0.60
1.56
0.49
B3LYP
6-311G(d,p)
1.55 1.79 4.62
10.31
7.50
22.44 0.37 0.95
0.60
1.58
0.46
MP2
6-31G(d) 1.57 1.67 4.40
9.09
6.46 19.94 0.41 0.97 0.61 1.61 0.46
6-31G(2d,p) 1.57 1.71
7.82
9.98
7.42 9.58 0.34 0.93 0.64 1.44 1.02
Exp. 1.53 2.24
9.38
12.58
11.73 14.92 0.07 0.74 0.79 0.94 0.84
The geometry was optimized at the indicated level of theory. Distances are given in (
˚
), densities
are given in (e/
˚
3
), and second derivatives are given in (e/
˚
5
)
Table 2 Bond topological properties at the BCP of the formal S1-N1 single bond in 1a,R
¼
Me
2
-
d
r
r
rl
1
l
l
e
d
N
ðÞ
d
S
ðÞ
d
N
ðÞ
d ðÞ
l
jj
l
3
2
3
B3PW91
6-31G(d,p)
1.75 1.31
8.46
6.94
6.34 4.81
0.09 0.98
0.77
1.27
1.44
6-31G(2d,p)
1.74 1.30
6.35
7.10
6.45 7.20
0.10 0.94
0.80
1.18
0.99
6-31G(3d,p)
1.73 1.36
8.49
7.32
6.65 5.49
0.10 0.98
0.75
1.31
1.33
6-311G(d,p)
1.75 1.32
8.58
7.32
6.71 5.45
0.09 0.95
0.80
1.19
1.34
6-311G(2d,p) 1.74 1.31
6.67
7.37
6.64 7.34
0.11 0.92
0.82
1.13
1.00
6-311G(3d,p) 1.73 1.36
8.85
7.56
6.86 5.56
0.10 0.95
0.77
1.23
1.36
cc-pVDZ
1.77 1.24
6.25
6.06
5.55 5.36
0.09 0.99
0.78
1.28
1.13
cc-pVTZ
1.73 1.38
9.95
7.84
6.98 4.88
0.12 0.94
0.79
1.20
1.61
B3LYP
6-311G(d,p) 1.75 1.30
8.40
7.32
6.74 5.67 0.09 0.95 0.80 1.18 1.29
Exp. 1.68 1.76
7.95
10.26
9.66 11.97 0.06 0.83 0.85 0.98 0.86
The geometry was optimized at the indicated level of theory. Distances are given in (
˚
), densities
in (e/
˚
3
), and second derivatives in (e/
˚
5
)
The bonds were selected as they possess different polarities. According to a
natural bond orbital/natural resonance theory (NBO/NRT) analysis [
50
] and on the
basis of the ratio
Me, Table
1
)
possesses a quite polar character. The S1-N1 single bond of the same compound
has also a polar character, while the S-C bond of compound 1a is less polar.
l
jj
l
3
=
, the S1
¼
N2 double bond of compound 1a (R
¼
