(HSi(Me)(2-PPh2–C6H4)2)Ni(PPh3) | 1331784-69-0

• 英文名称: (HSi(Me)(2-PPh2–C6H4)2)Ni(PPh3)
• 英文别名: (HSi(Me)(2-PPh₂-C₆H₄)₂)Ni(PPh₃)；(^PhPSi^HP)Ni(PPh₃)；[Ni(η2-Si,H-bis(o-(diphenylphosphino)phenyl)methylsilane-κ2P,P')(triphenylphosphine)]
• CAS: 1331784-69-0
• 化学式: C₅₅H₄₇NiP₃Si
• 分子量: 887.675
• InChiKey: ZHAWKARMHDLXEY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
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• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为产物：
  描述：

  bis(o-(diphenylphosphino)phenyl)methylsilane 以 氘代苯 、 甲苯 为溶剂， 反应 0.5h， 生成 (HSi(Me)(2-PPh2–C6H4)2)Ni(PPh3)
  参考文献：
  名称：

  Synthesis and reactivity of a masked PSiP pincer supported nickel hydride

  摘要：

  Tridentate PSiP pincer ligands featuring two phosphine donors and an anionic Si donor have attracted considerable attention in recent years. Here, we report the synthesis of the eta(3)-cyclooctenyl complex, ((PSiP)-P-Ph)Ni(eta(3)-cyclooctenyl) (1; (PSiP)-P-Ph = Si(Me)(2-PPh2-(CH4)-H-6)(2)) through the reaction of Ni(COD)(2) with (Ph)psi(H)p ((Ph)psi(H)p = HSi(Me)(2-PPh2-C6H4)(2)). We propose, that as a result of beta-hydride elimination of 1,3-COD, 1 can act as a synthetic equivalent for ((PSiP)-P-Ph)NiH. The reaction of 1 with a variety of different reagents including another equivalent of (Ph)PSi(H)p to form ((PSiP)-P-Ph)Ni-2 (2), 1,3-COD and H-2, PPh3 to form the Ni(0) species ((PSiP)-P-Ph-P-H)Ni(PPh3) (3) and 1,3-COD and 2,6-lutidine HCI to generate (PhPSiP)NiCI (4), 1,3-COD and H2 are in agreement with this hypothesis. In addition, in the reaction of 1 with BH3"THF, (PhPSiP)Ni(K2-BH4) (5) was observed but could not be isolated. This reaction presumably proceeds via (PhPSiP)NiH. This is supported by the observation that the reaction of (cYPSiP)NiH (cYPSiP = Si(Me)(2-PCY2-C6F14)2) with BH3.THF formed (cYPSiP)Ni(K2-BH4) (6). Catalytic reactions such as alkene isomerization and CO2 reduction using 1 as precatalyst are also consistent with a nickel hydride being accessible. Compounds 1, 2 and 6 were characterized by X-ray crystallography. (C) 2014 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.poly.2014.05.078

文献信息

• Reaction of bis(o-phosphinophenyl)silane with M(PPh3)4 (M = Ni, Pd, Pt): synthesis and structural analysis of η2-(Si–H) metal(0) and pentacoordinate silyl metal(ii) hydride complexes of the Ni triad bearing a PSiP-pincer ligand
  作者：Jun Takaya、Nobuharu Iwasawa

  DOI：10.1039/c1dt10526d

  日期：——

  Reactions of bis(o-(diphenylphosphino)phenyl)methylsilane with M(PPh3)4 (M = Ni, Pd, Pt) were investigated. When M = Ni or Pd, synthesis and isolation of η2-(Si-H) complexes of mononuclear Ni(0) and Pd(0) were achieved for the first time as frozen intermediates for oxidative addition of the Si–H bond. Structural analysis by X-ray and NMR spectroscopy disclosed that their η2-(Si–H) structures were maintained

  的反应 双（邻-（二苯基膦基）苯基）甲基硅烷用M（PPh 3）4（M = Ni，Pd，Pt）进行了研究。当M = Ni或钯，η的合成和分离2 -单核的Ni（0）和Pd（0）的（SI-H）络合物首次作为氧化加成的Si-H键的冷冻中间体得以实现。通过X射线和NMR结构分析光谱公开了他们的η 2 - （SI-H）结构保持在固体和溶液状态和Si-H键与金属中心的协调是相对较弱。另一方面，与铂（0）配合物反应得到了两种具有PSiP钳位配体的五配位甲硅烷基氢化铂（II）氢化物配合物，这些配合物经历了由方形金字塔形的独特热异构化顺式-H-Pt-Si转变为三角形-双锥体的反式-H-Pt-Si异构体。机理研究表明，该异构化着手通过可能通过旋转门旋转的分子内重排过程。