Electronic structure of dimethyl disulfide and naphthalene 1,8‐disulfide: Ab initio and E.S.C.A. results

Two diary1 disulfides, bis(2-pyrimidy1)disulfide and diphenyldisulfide, have been characterized by molecular mechanics and molecular orbital calculations. When complexed with Cu(I), the pyrimidyl disulfide is known to have a unique 180' C-S-S-C dihedral angle and to be coplanar. Our analysis of the conformational energies of the rotamers suggests that copper-ring interactions are primarily responsible for altering the molecular and electronic structure of the disulfide such that the trans barrier to rotation about the S-S bond is effectively overcome. In contrast, the phenyl and uncomplexed pyrimidyl disulfides prefer the usual C-S-S-C torsional angle near 8 5 O and have trans barriers greater than 7 kcal/mol. The barrier to rotation about S-Cspz bonds (2-3 kcal/mol) is low and consistent with ab initio calculations and experiments on other molecules. The force field calculations were done using M M P~. A serious problem was encountered in the use of the M M P l computer program on molecules with N,,a-type atoms that contribute only one electron to the a-electron system. A solution is to modify the variable electronegativity self-consistent field (VESCF) part of the M M P l calculation to use another set of parameters in the program that pertain to a type of nitrogen with one x electron. CND0/2 was used for most of the MO calculations, although INDO and extended Hiickel were also used.

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Some aspects of the photoelectron spectroscopy of organic sulfur compounds

Gleiter¹,

Spanget‐Larsen²

Topics in Current Chemistry

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Electronic structure of dimethyl disulfide and naphthalene 1,8‐disulfide: Ab initio and E.S.C.A. results

Cited by 8 publications

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ChemInform Abstract: ELECTRONIC STRUCTURE OF DIMETHYL DISULFIDE AND NAPHTHALENE 1,8‐DISULFIDE‐ AB INITIO AND E.S.C.A. RESULTS

ChemInform Abstract: ELECTRONIC STRUCTURE OF DIMETHYL DISULFIDE AND NAPHTHALENE 1,8‐DISULFIDE‐ AB INITIO AND E.S.C.A. RESULTS

Force field and self‐consistent field calculations on a trans coplanar disulfide: Bis(2‐pyrimidyl)disulfide

Some aspects of the photoelectron spectroscopy of organic sulfur compounds

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