Synthesis, X-ray crystal structures and spectroscopic properties of two binuclear platinum(III) dithiocarboxylate complexes

Abstract

Two binuclear platinum(III) dithiocarboxylato-derivatives [Pt₂(RCS₂)₄l₂][R = PhCH₂(1), Me₂CH (2)] have been synthesized and characterized. The complex (2) crystallizes in two forms, one of which, (2a), includes molecular iodine in the unit cell. The crystal structures of compounds (1) and (2a) have been determined and their main feature is that the molecular units are dimeric, with Pt–Pt distances of 2.598(2)Å for compound (1) and 2.578(1)Å for compound (2a); the Pt–I distances were 2.753(3) and 2.763 Å(mean) for compounds (1) and (2a), respectively. Both Pt–Pt distances are shorter than those found in the corresponding unoxidized starting compounds. This is in agreement with an electronic configuration (d_σ)². The relationship between the metal–metal distance and oxidation state is discussed.