INVESTIGADORES
ROMANO rosana mariel
artículos
Título:
Anomeric and mesoneric effects in methoxycarbonylsulfenyl chloride, CH3OC(O)SCl. An experimental and theoretical study
Autor/es:
MAURICIO F. ERBEN; CARLOS O. DELLA VÉDOVA; ROSANA M. ROMANO; ROLAND BOESE; HEINS OBERHAMMER; HELGE WILLNER; OSWALDO SALA
Revista:
INORGANIC CHEMISTRY
Referencias:
Año: 2002 vol. 41 p. 1064 - 1071
ISSN:
0020-1669
Resumen:
The molecular structure and conformational properties of methoxycarbonylsulfenyl chloride, CH3OC(O)SCl, were
determinated in the gas and solid phases by gas electron diffraction, low-temperature X-ray diffraction, and vibrational
spectroscopy. Furthermore, quantum chemical calculations were performed. Experimental and theoretical methods
result in structures with a planar C-O-C(O)-S-Cl skeleton. The electron diffraction intensities are reproduced
best with a mixture of 72(8)% syn and 28(8)% anti conformers (S-Cl bond synperiplanar/antiperiplanar with respect
to CdO bond) and the O-CH3 bond synperiplanar with respect to the CdO bond. The syn form is the preferred
form and becomes the exclusive form in the crystalline solid at low temperature. This experimental result is reproduced
very well by Hartree-Fock approximation and by density functional theory at different levels of theory but not by
the MP2/6-311G* method, which overestimates the value of ¢G° between the syn and anti conformers. The results
are discussed in terms of anomeric effects and a natural bond orbital (NBO) calculation. Photolysis of matrixisolated
CH3OC(O)SCl with broad-band UV-visible irradiation produces an interconversion of the conformers, and
the concomitant decomposition leads to formation of OCS and CO molecules.3OC(O)SCl, were
determinated in the gas and solid phases by gas electron diffraction, low-temperature X-ray diffraction, and vibrational
spectroscopy. Furthermore, quantum chemical calculations were performed. Experimental and theoretical methods
result in structures with a planar C-O-C(O)-S-Cl skeleton. The electron diffraction intensities are reproduced
best with a mixture of 72(8)% syn and 28(8)% anti conformers (S-Cl bond synperiplanar/antiperiplanar with respect
to CdO bond) and the O-CH3 bond synperiplanar with respect to the CdO bond. The syn form is the preferred
form and becomes the exclusive form in the crystalline solid at low temperature. This experimental result is reproduced
very well by Hartree-Fock approximation and by density functional theory at different levels of theory but not by
the MP2/6-311G* method, which overestimates the value of ¢G° between the syn and anti conformers. The results
are discussed in terms of anomeric effects and a natural bond orbital (NBO) calculation. Photolysis of matrixisolated
CH3OC(O)SCl with broad-band UV-visible irradiation produces an interconversion of the conformers, and
the concomitant decomposition leads to formation of OCS and CO molecules.-O-C(O)-S-Cl skeleton. The electron diffraction intensities are reproduced
best with a mixture of 72(8)% syn and 28(8)% anti conformers (S-Cl bond synperiplanar/antiperiplanar with respect
to CdO bond) and the O-CH3 bond synperiplanar with respect to the CdO bond. The syn form is the preferred
form and becomes the exclusive form in the crystalline solid at low temperature. This experimental result is reproduced
very well by Hartree-Fock approximation and by density functional theory at different levels of theory but not by
the MP2/6-311G* method, which overestimates the value of ¢G° between the syn and anti conformers. The results
are discussed in terms of anomeric effects and a natural bond orbital (NBO) calculation. Photolysis of matrixisolated
CH3OC(O)SCl with broad-band UV-visible irradiation produces an interconversion of the conformers, and
the concomitant decomposition leads to formation of OCS and CO molecules.-Cl bond synperiplanar/antiperiplanar with respect
to CdO bond) and the O-CH3 bond synperiplanar with respect to the CdO bond. The syn form is the preferred
form and becomes the exclusive form in the crystalline solid at low temperature. This experimental result is reproduced
very well by Hartree-Fock approximation and by density functional theory at different levels of theory but not by
the MP2/6-311G* method, which overestimates the value of ¢G° between the syn and anti conformers. The results
are discussed in terms of anomeric effects and a natural bond orbital (NBO) calculation. Photolysis of matrixisolated
CH3OC(O)SCl with broad-band UV-visible irradiation produces an interconversion of the conformers, and
the concomitant decomposition leads to formation of OCS and CO molecules.dO bond) and the O-CH3 bond synperiplanar with respect to the CdO bond. The syn form is the preferred
form and becomes the exclusive form in the crystalline solid at low temperature. This experimental result is reproduced
very well by Hartree-Fock approximation and by density functional theory at different levels of theory but not by
the MP2/6-311G* method, which overestimates the value of ¢G° between the syn and anti conformers. The results
are discussed in terms of anomeric effects and a natural bond orbital (NBO) calculation. Photolysis of matrixisolated
CH3OC(O)SCl with broad-band UV-visible irradiation produces an interconversion of the conformers, and
the concomitant decomposition leads to formation of OCS and CO molecules.-Fock approximation and by density functional theory at different levels of theory but not by
the MP2/6-311G* method, which overestimates the value of ¢G° between the syn and anti conformers. The results
are discussed in terms of anomeric effects and a natural bond orbital (NBO) calculation. Photolysis of matrixisolated
CH3OC(O)SCl with broad-band UV-visible irradiation produces an interconversion of the conformers, and
the concomitant decomposition leads to formation of OCS and CO molecules.¢G° between the syn and anti conformers. The results
are discussed in terms of anomeric effects and a natural bond orbital (NBO) calculation. Photolysis of matrixisolated
CH3OC(O)SCl with broad-band UV-visible irradiation produces an interconversion of the conformers, and
the concomitant decomposition leads to formation of OCS and CO molecules.3OC(O)SCl with broad-band UV-visible irradiation produces an interconversion of the conformers, and
the concomitant decomposition leads to formation of OCS and CO molecules.