Synthesis, Molecular and Crystal Structures of the [Pt2Cl6(PPh3)2] Complex

The synthesis and crystal structure are described of new bimetallic platinum complex [Pt2Cl6(PPh3)2] (1) obtained by partial reduction of hexachloroplatinic acid H2[PtCl6] in the presence of triphenylphosphine and sodium hydrocarbonate in tetrahydrofuran. The complex is isolated as an intermediate reaction product. It is found that the crystal structure of complex 1 contains two platinum atoms in different coordination environments: Pt1 has the square planar geometry and Pt2 is a distorted tetragonal bipyramid. It is indicative of the presence of platinum in mixed oxidation states (II/IV). The molecules are packed mainly by C–H⋯Cl interactions in the crystal, as confirmed by the analysis of Hirshfeld surfaces and 2D fingerprints. The data obtained expand our knowledge about the intermediate products of H2[PtCl6] reduction and can be useful for understanding the mechanisms of homogeneous catalysis based on platinum complexes, particularly in hydrosilylation and silicone vulcanization reactions.