Table 3 Selected geometrical parameters, relative electronic energies, relative energies at 0 K and 15N and 13C NMR chemical shifts calculated for the most
stable conformers of the compounds 1A, 1B, 3A, and 3Ba
Dihedral angles/°
Chemical shifts [ppm]
O–C–N–O
C–N–O–C
N–O–C–O
Erel/kJ mol−1
Erel(0 K)/kJ mol−1
(N)b
(N–CO)c
(O–CO)c
1Aa
1Ba
3Aa
3Ba
−11.9
0.0
−6.8
0.0
−79.7
180.0
−82.3
180.0
−8.3
180.0
−8.5
0/−437.172086d
11.06
0/−437.057445e
12.10
−217.0
−80.8
−217.8
−78.1
175.1
166.7
175.1
164.2
179.7
176.1
179.8
176.4
0/−628.953421d
11.85
0/−628.785322e
11.88
180.0
a Energies are related to the most stable isomers of the given molecules (1a and 3a, respectively). Total electronic energies as well as energies at 0 K in Hartrees
are given only for most stable isomers 1a and 3a, respectively. b Chemical shifts of nitrogen atoms are related to the calculated value for nitromethane (−152.4).
c Chemical shifts of carbon atoms are related to the calculated value for TMS (184.0). d B3LYP/6-311+G(d,p) total electronic energy in Hartrees. e B3LYP/6-
311+G(d,p) energy at 0 K (includes zero point vibrational energy) in Hartrees.
Table 4 Widths of selected 1H, 13C and 15N NMR lines of R–C(O)–NH–O–
16 O. Exner, in The Chemistry of Functional Groups. The Chemistry of
Peroxides, ed. S. Patai, Interscience, New York, 1983, p. 85.
17 A. Bagno, C. Comuzzi and G. Scorrano, J. Am. Chem. Soc., 1994, 116,
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C(O)–R′ in DMSO solutionsa
C(O)–HN–O–C(O)
18 M. Tkadlecová, M. Kvíčalová, L. Soukupová, V. Blechta, J. Schraml
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Compd.
R
R′
1H
15N
13C–N
13C–O
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1
2
3
4
Me
Me
Ph
Me
Ph
Me
Ph
4.9
7.5
2.9
2.8
5.4
2.8
2.9
4.9
5.0
2.1
2.2
0.7
1.2
14
16
20
Ph
a The linewidths in Hz, the 13C and 15N data are from concentrated solutions
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2 3 1 4
O r g . B i o m o l . C h e m . , 2 0 0 4 , 2 , 2 3 1 1 – 2 3 1 4