monocarbonyl(η5-1,2,3,4,5-pentamethylcyclopentadienyl)(1,2-bis(dimethylphosphino)ethane)(benzyl)molybdenum | 765908-53-0

• 英文名称: monocarbonyl(η5-1,2,3,4,5-pentamethylcyclopentadienyl)(1,2-bis(dimethylphosphino)ethane)(benzyl)molybdenum
• CAS: 765908-53-0
• 化学式: C₂₄H₃₈MoOP₂
• 分子量: 500.453
• InChiKey: CQQDNMMDIJUPFG-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：

  (η5-1,2,3,4,5-pentamethylcyclopentadienyl)(1,2-bis(dimethylphosphino)ethane)(η3-benzyl)molybdenum 、 一氧化碳 以 苯 为溶剂， 以21%的产率得到monocarbonyl(η5-1,2,3,4,5-pentamethylcyclopentadienyl)(1,2-bis(dimethylphosphino)ethane)(benzyl)molybdenum
  参考文献：
  名称：

  Silylene Hydride Complexes of Molybdenum with Silicon−Hydrogen Interactions:  Neutron Structure of (η⁵-C₅Me₅)(Me₂PCH₂CH₂PMe₂)Mo(H)(SiEt₂)

  摘要：

  Reduction of Cp*MoCl4 with 3.1 equiv of Na/Hg amalgam (1.0% w/w) in the presence of 1 equiv of dmpe and 1 equiv of trimethylphosphine afforded the molybdenum(II) chloride complex Cp*(dmpe)(PMe3)MoCl (1) (Cp* = 1,2,3,4,5-pentamethylcyclopentadienyl, dmpe = 1,2-bis(dimethylphosphino)ethane). Alkylation of 1 with PhCH2MgCl proceeded in high yield to liberate PMe3 and give the 18-electron z-benzyl complex Cp*(dmpe)Mo(eta(3)-CH2Ph) (2). Variable temperature NMR experiments provided evidence that 2 is in equilibrium with its 16-electron eta(1)-benzyl isomer [Cp*(dmpe)Mo(eta(1)-CH2Ph)]. This was further supported by reaction of 2 with CO to yield the carbonyl benzyl complex Cp*(dmpe)(CO)Mo(eta(1)-CH2Ph) (3). Complex 2 was found to react with disubstituted silanes H2SiRR' (RR' = Me-2, Et-2, MePh, and Ph-2) to form toluene and the silylene complexes Cp*(dmpe)Mo(H)(SiRR') (4a: RR = Me-2; 4b: RR' = Et-2; 4c: RR' = MePh; 4d: RR' = Ph-2). Reactions of 2 with monosubstituted silanes H3SiR (R = Ph, Mes, Mes = 2,4,6-trimethylphenyl) produced rare examples of hydrosilylene complexes Cp*(dmpe)Mo(H)Si(H)R (5a: R = Ph; 5b: R = Mes; 5c: R = CH2Ph). Reactivity of complexes 4a-c and 5a-d is dominated by 1,2-hydride migration from metal to silicon, and these complexes possess (HSi)-Si-... bonding interactions, as supported by spectroscopic and structural data. For example, the J(HSi) coupling constants in these species range in value from 30 to 48 Hz and are larger than would be expected in the absence of (HSi)-Si-... bonding. A neutron diffraction study on a single crystal of diethylsilylene complex 4b unequivocally determined the hydride ligand to be in a bridging position across the molybdenum-silicon bond (Mo-H 1.85(1) Angstrom, Si-H 1.68(1) A). The synthesis and reactivity properties of these complexes are described in detail.

  DOI：

  10.1021/ja040026g