Syntheses of selenolato-bridged dinuclear hydridoplatinum complexes [Pt2H2(μ-SetBu)2(PPh 3)2] and [Pt2H(SetBu)(μ-Se tBu)2(PPh3)2]: Unusual thermal reaction of hydrido(1,1-dimethylethaneselenolato)

Article abstract of DOI:10.1021/ic1011742

Novel selenolato-bridged dinuclear hydridoplatinum complexes, cis-[Pt ₂H₂(μ-Se^tBu)₂(PPh ₃)₂] (2) and cis-[Pt₂H(Se^tBu)(μ- Se^tBu)₂(PPh₃)₂] (3) were synthesized in 30% and 57% yields, respectively, by the thermolysis of hydrido(1,1- dimethylethaneselenolato) Pt(II) complex cis-[PtH(Se^tBu)(PPh ₃)₂] (1) in toluene at 80 °C for 3 h. The structures of dinuclear complexes 2 and 3 were fully characterized on the basis of their NMR and IR spectroscopic data and X-ray crystallography. The two distorted square planar Pt atoms in 2 and 3 are held together by two bridged selenolato ligands, ^tBu groups of which adopt a trans configuration with respect to the four-membered Pt₂Se₂ ring. Each central Pt ₂Se₂ ring in 2 and 3 has a hinged arrangement due to the steric repulsion among the two PPh₃ ligands and the ^tBu group lying between them.