Ligand Exchange of Diplatinum Complexes with Bridging Silyl Ligands Involving Si−H Bond Cleavage and Formation
Ligand Exchange of Diplatinum Complexes with Bridging Silyl Ligands Involving Si−H Bond Cleavage and Formation
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DOI：
10.1021/om7012869
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发表时间：
2008-04
期刊：
影响因子：
2.8
通讯作者：
M. Tanabe;D. Ito;K. Osakada
中科院分区：
文献类型：
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作者：
M. Tanabe;D. Ito;K. Osakada
在室温下，过量的H2SiEt 2和H2SiHex 2与[Pt（PCy 3）2]反应形成单核顺式-双（甲硅烷基）铂络合物，顺式-[Pt（H）（SiHR 2）（PCy 3）2]（1：R = Et，2：R = Hex），其被转化为具有桥接二烷基甲硅烷基配体的双铂络合物，[{Pt（PCy 3）}2（μ-η2-HSiR2）2]（3：R = Et，4：R = Hex）。配合物3与过量的H_2SiPhMe和H_2SiPh_2反应，通过桥连甲硅烷基配体的交换得到双核配合物[{Pt（PCy_3）}_2（μ-η_2-HSiPhR）_2]（5：R = Me，6：R = Ph）。H2SiPh 2与3的等摩尔反应产生双铂络合物[{Pt（PCy 3）}2（μ-η 2-HSiEt 2）（μ-η 2-HSiPh 2）]（7）和[{Pt（PCy 3）}2（μ-η2：η2-H2SiEt 2）（μ-SiPh 2）]（8）的混合物。在反应中使用D2 SiPh 2导致氘在7的二乙基甲硅烷基和二苯基甲硅烷基配体、8的二乙基甲硅烷基配体和6的二苯基甲硅烷基配体中的分布。配合物6分别与dmpe（1，2-双（二苯基膦基）乙烷）和dppe（1，2-双（二苯基膦基）乙烷）进行了配体交换反应
Reactions of excess H2SiEt2 and H2SiHex2 with [Pt(PCy3)2] at room temperature form mononuclear cis-hydrido(silyl)platinum complexes, cis-[Pt(H)(SiHR2)(PCy3)2] (1: R = Et, 2: R = Hex), which are converted into diplatinum complexes with bridging dialkylsilyl ligands, [{Pt(PCy3)}2(µ-η2-HSiR2)2] (3: R = Et, 4: R = Hex), upon heating at 80 °C. Complex 3 reacts with excess H2SiPhMe and H2SiPh2 to afford dinuclear complexes [{Pt(PCy3)}2(µ-η2-HSiPhR)2] (5: R = Me, 6: R = Ph) via exchange of the bridging silyl ligands. An equimolar reaction of H2SiPh2 with 3 yields a mixture of diplatinum complexes [{Pt(PCy3)}2(µ-η2-HSiEt2)(µ-η2-HSiPh2)] (7) and [{Pt(PCy3)}2(µ-η2:η2-H2SiEt2)(µ-SiPh2)] (8). Use of D2SiPh2 in the reaction results in distribution of deuterium in the diethylsilyl and diphenylsilyl ligands of 7, the diethylsilane ligand of 8, and the diphenylsilyl ligand of 6. Complex 6 undergoes exchange of the phosphine ligands with dmpe (1,2-bis(dimethylphosphino)ethane) and with dppe (1,2-bis(diphenylphosphino)etha...