Abstract

cis-[PtL 2R 2] (L = Me 2SO or Me 2S; R = Me or Ph) species react with N,N′-disubstituted dithioxamides H 2-R′ 2-DTO (R′ = methyl, benzyl, n-butyl) leading to a new class of organoplatinum compounds of general formula [PtL(R)(H-R′2-DTO)] ( 1). These are the first reported organometallic complexes containing an S,S′ Pt chelated rubeanate. The new compounds react with some neutral ligands L′ (L′= carbon monoxide, phosphines and thioureas) giving [PtL′(R)(H-R′ 2-DTO)] ( 2) products, which are totally unreactive toward nitrogen bases such as amines, pyridines and anilines. The compound trans-[Pt(Me 2SO) 2MeCl] reacts with H 2-bz 2-DTO forming the contact ion pair {Pt(Me 2SO)Me(H 2-bz 2-DTO) +,(Cl −)} ( 3); this is a non-isolable species since the PtCH 3 bond is cleaved by acidic hydrogens of the coordinated neutral dithioxamide leading to the formation of methane and [Pt(Me 2SO)Cl(H-bz 2-DTO)] ( 4). A structure for the tight ion pair {Pt(Me 2SO)Me(H 2-bz 2-DTO) +,(Cl −)} is proposed in which the coordinated neutral dithioxamide acts as an anion binding agent.

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