DISTORTION COORDINATE FOR NONRIGID FIVE- COORDINATED GERMANIUM. SYNTHESIS AND MOLECULAR STRUCTURE OF SPIROCYCLIC ANIONIC METHYLGERMANATES VARYING IN RING COMPOSITION′

Abstract

Abstract Reaction of an organogermanium trichloride with a catechol or thiocatechol derivative in the presence of triethylamine, followed by a metathetical exchange, led to the isolation of the Et,N′ salts of the five-coordinated spirocyclic germanates [(C,H,0,),GeMe][Et,N] (1), [(MeC,H3S2_)2GeMe][Et,N] (2), [(C,CI,O,), GeMe][Et,N] (3), and [(C,H,S,), GePh][Et,N] (4). X-ray analysis showed that the geometry of 1 is close to a trigonal bipyramid, 2 is displaced about one-third toward the rectangular pyramid, and 3 is close to the rectangular pyramid. The low structural displacement for 1 is attributed to lattice effects. The structures of 2 and 3 are discussed in terms of ligand effects, the insertion of ring sulfur atoms in 2, and the electron-withdrawing effect of chlorine ring atoms in 3. The structures of these and related anionic germanates follow the local C2, constraint of the Berry pseudorotational coordinate with a trans basal angle, 0, for the “limiting” RP of 150.1°, similar to that for other ma...