THEORETICAL-STUDIES ON THE STRUCTURE AND ELECTRONIC-PROPERTIES OF ARYL SULFIDES AND SULFONES

Molecular orbital calculations are reported on the structure and elect ronic properties of diphenyl sulfide using both semiempirical and ab i nitio methods. Neither the MNDO nor AM1 methods give satisfactory stru ctures, but better results are obtained with the PM3 method. At the ab initio level, the 4-31G basis set with polarization functions on sulf ur alone (4-31G/S) gives comparable results-to those obtained with th e 6-31G* basis set. The corresponding bond lengths and angles at the sulfur atom of 4-aminophenyl-4'-nitrophenyl sulfide and related deriva tives of diphenyl sulfone, diphenyl disulfide, and phenylthiosulfonate calculated at the 4-31 G/S level show a good correlation with crysta llographic data where available. (C) 1998 John Wiley & Sons, Inc.