Département de chimie moléculaire

Dissoln. of [S4N3]Cl in liq. ammonia produces a reactive soln. which on treatment with cis [PtCl2(PR3)2] gives [S2N2]2- complexes in 32-76{%} yields. Similarly, SeCl4 and [S4N3]Cl in a ratio of 5:1 react cleanly with cis-[PtCl2{\{}P(OMe)nPh3-n{\}}] to give the desired selenosulfur dinitrido, [SeSN2]2- complexes with no phosphorus contg. starting material evident by 31P NMR spectroscopy. The new complexes were characterized by IR, 31P NMR, microanal. and X-ray crystallog. with nine crystal structures being reported. In 31P nmr the 1J PtP coupling consts. are influenced by the oxygen content of their phosphorus ligands. In the mixed chalcogen complexes the Pt-N bond lengths appear to follow a simple trend as a consequence of the electronic properties of the phosphorus ligand and these trends can be interpreted empirically by examn. of the LUMO but are not well supported by DFT calcns. [on SciFinder(R)]