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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posted on 2010-09-06, 00:00 authored by Norio Nakata, Takashige Ikeda, Akihiko IshiiNovel selenolato-bridged dinuclear hydridoplatinum complexes, <i>cis</i>-[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>] (<b>2</b>) and <i>cis</i>-[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>] (<b>3</b>) were synthesized in 30% and 57% yields, respectively, by the thermolysis of hydrido(1,1-dimethylethaneselenolato) Pt(II) complex <i>cis</i>-[PtH(Se<sup><i>t</i></sup>Bu)(PPh<sub>3</sub>)<sub>2</sub>] (<b>1</b>) in toluene at 80 °C for 3 h. The structures of dinuclear complexes <b>2</b> and <b>3</b> 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 <b>2</b> and <b>3</b> are held together by two bridged selenolato ligands, <sup><i>t</i></sup>Bu groups of which adopt a trans configuration with respect to the four-membered Pt<sub>2</sub>Se<sub>2</sub> ring. Each central Pt<sub>2</sub>Se<sub>2</sub> ring in <b>2</b> and <b>3</b> has a hinged arrangement due to the steric repulsion among the two PPh<sub>3</sub> ligands and the <sup><i>t</i></sup>Bu group lying between them.
