PM3 study of organometallic radicals formed by elements in periodic Groups 13–16

Abstract

Calculations have been made by the PM3 SCF method of the molecular and electronic structures of a range of neutral, cationic and anionic organometallic radicals derived from permethyl derivatives of elements from Groups 13–16. In Group 13, the planar methyls M(CH 3) 3 all yield pyramidal mononuclear radical-anions [M(CH 3) 3] −, but only for M = Al was a stable dinuclear radical-anion [Al 2(CH 3) 6] − found; this is a weak complex of [Al(CH 3) 2] . and [Al(CH 3) 4] −.In Group 14, dinuclear σ radical-cations [M 2(CH 3) 6] + of D 3 d symmetry are found for M = SiPb, and analogous * radical-cations are found for M = PBi in Group 15. The dinuclear [M 2(CH 3) 4] + formed by sulphur and selenium both have C 2 h symmetry.