Activation of Homolytic SiZn and SiHg Bond Cleavage,Mediated by a Pt0 Complex,via Novel PtZn and PtHg Compounds |
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| Authors: | Yosi Kratish Dr Gregory Molev Arseni Kostenko Dr Dennis Sheberla Dr Boris Tumanskii Dr Shigeru Shimada Dr Dmitry Bravo‐Zhivotovskii Prof?Dr Yitzhak Apeloig |
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| Institution: | 1. Schulich Faculty of Chemistry and the Lise Meitner‐Minerva Center for Computational Quantum Chemistry, Technion‐Israel Institute of Technology, Haifa 32000 (Israel);2. Interdisciplinary Research Center for Catalytic Chemistry, National Institute of Advanced Industrial Science and Technology (AIST), Central 5, 1‐1‐1 Higashi, Tsukuba, Ibaraki 305‐8565 (Japan) |
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| Abstract: | The thermally stable (tBuMe2Si)2M] (M=Zn, Hg) generate R3Si. radicals in the presence of (dmpe)Pt(PEt3)2] at 60–80 °C. The reaction proceeds via hexacoordinate Pt complexes, (M=Zn ( 2 a and 2 b ), M=Hg ( 3 a and 3 b )) which were isolated and characterized. Mild warming or photolysis of 2 or 3 lead to homolytic dissociation of the Pt? MSiR3 bond generating silyl radicals and novel unstable pentacoordinate platinum paramagnetic complexes (M=Zn ( 5 ), Hg ( 6 )) whose structures were determined by EPR spectroscopy and DFT calculations. |
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| Keywords: | mercury platinum silyl radicals trinuclear complexes zinc |
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