suppmat_table. 68KB Jun 05 2011 09:30:54 PM
page 3
Table S1. Mulliken and Natural Bond Orbital (NBO) population analysis (net atomic charges, q and bond
orbital population, bop) of CXNO (X = Cl, Br) species in their 1A′′ ground states (3A″″ ground state for halocarbonylnitrenes), computed at the B3LYP/ 6-31G(d,p) level of theory.
bop
q
CXNO
X
C
N
O
ClNCO
0.17
0.70
-0.52
-0.35
(0.17)
BrNCO
0.13
(0.24)
ClOCN
0.23
(0.24)
BrOCN
0.24
(0.31)
ClCNO(linear)
ClCNO(bent)
BrCNO(linear)
(0.85) (-0.58) (-0.44)
0.71
-0.48
X-N
X-C
X-O
C-N
C-O
0.09
0.49
0.61
0.16
0.44
0.61
0.07
0.77
0.28
0.11
0.78
0.27
N-O
a
-0.36
(0.84) (-0.64) (-0.45)
0.57
-0.37
-0.44
(0.55) (-0.34) (-0.45)
0.58
-0.38
-0.44
(0.55) (-0.36) (-0.50)
0.19
0.13
(0.14)
(0.08)
0.17
0.07
(0.13)
(0.08)
0.06
0.26
0.16
-0.47
0.21
0.57
0.38
0.22
0.59
0.37
0.28
0.53
0.36
0.24
0.20
0.51
0.27
0.38
0.31
0.25
0.20
0.52
0.30
0.38
0.31
(0.16) (-0.38)
0.21
-0.45
(0.16) (-0.37)
0.15
-0.47
(0.23) (-0.01) (0.16) (-0.38)
3
ClC(O)N( A″)
0.03
0.38
-0.12
-0.29
(-0.03) (0.46) (-0.02) (-0.41)
1
ClC(O)N( A′)
0.11
(0.06)
3
BrC(O)N( A″)
-0.05
(0.01)
BrC(O)N(1A′)
0.00
(0.12)
ClONC
0.21
(0.21)
BrONC
0.22
(0.27)
ClN(O)C
0.12
(0.12)
BrN(O)C
0.09
(0.17)
a
0.45
-0.23
-0.34
(0.43) (-0.11) (-0.39)
0.49
-0.13
-0.30
(0.43) (-0.04) (-0.41)
0.57
-0.23
-0.34
(0.37) (-0.11) (-0.39)
0.04
0.11
-0.36
0.06
0.60
0.12
0.10
0.60
0.11
(0.28) (-0.23) (-0.26)
0.02
0.12
-0.36
(0.26) (-0.22) (-0.31)
0.28
-0.22
-0.18
0.08
0.09
0.24
0.001
0.13
0.09
0.23
-0.004
(0.46) (-0.26) (-0.33)
0.28
-0.18
-0.18
(0.46) (-0.30) (-0.33)
Figures in parentheses are the natural charges
Table S1. Mulliken and Natural Bond Orbital (NBO) population analysis (net atomic charges, q and bond
orbital population, bop) of CXNO (X = Cl, Br) species in their 1A′′ ground states (3A″″ ground state for halocarbonylnitrenes), computed at the B3LYP/ 6-31G(d,p) level of theory.
bop
q
CXNO
X
C
N
O
ClNCO
0.17
0.70
-0.52
-0.35
(0.17)
BrNCO
0.13
(0.24)
ClOCN
0.23
(0.24)
BrOCN
0.24
(0.31)
ClCNO(linear)
ClCNO(bent)
BrCNO(linear)
(0.85) (-0.58) (-0.44)
0.71
-0.48
X-N
X-C
X-O
C-N
C-O
0.09
0.49
0.61
0.16
0.44
0.61
0.07
0.77
0.28
0.11
0.78
0.27
N-O
a
-0.36
(0.84) (-0.64) (-0.45)
0.57
-0.37
-0.44
(0.55) (-0.34) (-0.45)
0.58
-0.38
-0.44
(0.55) (-0.36) (-0.50)
0.19
0.13
(0.14)
(0.08)
0.17
0.07
(0.13)
(0.08)
0.06
0.26
0.16
-0.47
0.21
0.57
0.38
0.22
0.59
0.37
0.28
0.53
0.36
0.24
0.20
0.51
0.27
0.38
0.31
0.25
0.20
0.52
0.30
0.38
0.31
(0.16) (-0.38)
0.21
-0.45
(0.16) (-0.37)
0.15
-0.47
(0.23) (-0.01) (0.16) (-0.38)
3
ClC(O)N( A″)
0.03
0.38
-0.12
-0.29
(-0.03) (0.46) (-0.02) (-0.41)
1
ClC(O)N( A′)
0.11
(0.06)
3
BrC(O)N( A″)
-0.05
(0.01)
BrC(O)N(1A′)
0.00
(0.12)
ClONC
0.21
(0.21)
BrONC
0.22
(0.27)
ClN(O)C
0.12
(0.12)
BrN(O)C
0.09
(0.17)
a
0.45
-0.23
-0.34
(0.43) (-0.11) (-0.39)
0.49
-0.13
-0.30
(0.43) (-0.04) (-0.41)
0.57
-0.23
-0.34
(0.37) (-0.11) (-0.39)
0.04
0.11
-0.36
0.06
0.60
0.12
0.10
0.60
0.11
(0.28) (-0.23) (-0.26)
0.02
0.12
-0.36
(0.26) (-0.22) (-0.31)
0.28
-0.22
-0.18
0.08
0.09
0.24
0.001
0.13
0.09
0.23
-0.004
(0.46) (-0.26) (-0.33)
0.28
-0.18
-0.18
(0.46) (-0.30) (-0.33)
Figures in parentheses are the natural charges