通过新型 Pt-Zn 和 Pt-Hg 化合物，Pt(0) 配合物介导的 Si-Zn 和 Si-Hg 键均裂的活化。
Activation of Homolytic Si-Zn and Si-Hg Bond Cleavage, Mediated by a Pt(0) Complex, via Novel Pt-Zn and Pt-Hg Compounds.
机构信息
Schulich Faculty of Chemistry and the Lise Meitner-Minerva Center for Computational Quantum Chemistry, Technion-Israel Institute of Technology, Haifa 32000 (Israel).
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).
出版信息
Angew Chem Int Ed Engl. 2015 Sep 28;54(40):11817-21. doi: 10.1002/anie.201505805. Epub 2015 Aug 18.
The thermally stable [(tBuMe2 Si)2 M] (M=Zn, Hg) generate R3 Si(.) 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.
[(tBuMe2 Si)2 M]（M=Zn、Hg）在 60-80°C 下存在[(dmpe)Pt(PEt3 )2 ]时会生成 R3 Si(.)自由基。该反应通过六配位 Pt 配合物（M=Zn（2a 和 2b），M=Hg（3a 和 3b））进行，这些配合物已被分离和表征。温和加热或光解 2 或 3 会导致 Pt-MSiR3 键的均裂，生成硅自由基和新型不稳定的五配位铂顺磁性配合物（M=Zn（5），Hg（6）），其结构通过 EPR 光谱和 DFT 计算确定。
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