Syntheses of Selenolato-Bridged Dinuclear Hydridoplatinum Complexes [Pt<sub>2</sub>H<sub>2</sub>(μ-Se<sup><i>t</i></sup>Bu)<sub>2</sub>(PPh<sub>3</sub>)<sub>2</sub>] and [Pt<sub>2</sub>H(Se<sup><i>t</i></sup>Bu)(μ-Se<sup><i>t</i></sup>Bu)<sub>2</sub>(PPh<sub>3</sub>)<sub>2</sub>]: Unusual Thermal Reaction of Hydrido(1,1-Dimethylethaneselenolato) Platinum Complex <i>cis</i>-[PtH(Se<sup><i>t</i></sup>Bu)(PPh<sub>3</sub>)<sub>2</sub>]
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Novel selenolato-bridged dinuclear hydridoplatinum complexes, cis-[Pt2H2(μ-SetBu)2(PPh3)2] (2) and cis-[Pt2H(SetBu)(μ-SetBu)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(SetBu)(PPh3)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 Pt2Se2 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.
