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The activation of Ph2HSiSiHPh2 and Me3SiSiMe3 at [Pt(PEt3)3] (1) yielded the products of oxidative addition. The formation of [Pt(SiHPh2)2(PEt3)2] (2) as a mixture of the cis and trans isomers appears to proceed quantitatively, whereas a conversion to give cis-[Pt(SiMe3)2(PEt3)2] (3) was not complete. Treatment of 1 with one equivalent of H2SiPh2 led to cis-and trans-[Pt(H)(SiHPh2)(PEt3)2] (cis-4, trans-4) together with the dinuclear complex [(Et3P)2(H)Pt(μ-SiPh2)(μ–η2-HSiPh2)Pt(PEt3)] (5). In contrast, HSiMe3 reacts with [Pt(PEt3)3] to yield cis-[Pt(H)(SiMe3)(PEt3)2] (7) exclusively. Catalytic reactions of dihydrogen with the disilanes Ph2HSiSiHPh2 or Me3SiSiMe3 in the presence of catalytic amounts of [Pt(PEt3)3] (1) led to the products of hydrogenolysis, H2SiPh2 and HSiMe3. The conversion of Me3SiSiMe3 is much slower and needs higher temperature to proceed.
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