cis-[Mo(CO)2(η5:η1-C5H4(CH2)2PPh2)(NCCD3)] | 709674-82-8

• 英文名称: cis-[Mo(CO)2(η5:η1-C5H4(CH2)2PPh2)(NCCD3)]
• CAS: 709674-82-8；710293-53-1
• 化学式: BF₄*C₂₃H₂₁MoNO₂P
• 分子量: 560.12
• InChiKey: NOABZWDTXNRAHU-OXNJQWINSA-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：

  氘代乙腈 、 [HMo(CO)2[η5:η1-C5H4(CH2)2PPh2]]*0.2toluene 、 trityl tetrafluoroborate 以 氘代乙腈 为溶剂， 生成 cis-[Mo(CO)2(η5:η1-C5H4(CH2)2PPh2)(NCCD3)] 、 cis-[Mo(CO)2(η5:η1-C5H4(CH2)2PPh2)(NCCD3)]
  参考文献：
  名称：

  Molybdenum Carbonyl Complexes in the Solvent-Free Catalytic Hydrogenation of Ketones

  摘要：

  The heterodifunctional ligand Li[eta(5)-C5H4(CH2)(2)PR2] (R = Ph, Cy, and Bu-t) reacts with MO(CO)(3)(diglyme) to give the molybdenum anion complex Li{Mo(CO)(3) [eta(5)-C5H4(CH2)(2)PR2]}. Protonation with HOAc gives the metal hydride complexes HMo(CO)(2)[eta(5):eta(1)-C5H4(CH2)(2)PR2], in which the phosphine and cyclopentadienyl ligands are linked by a two-carbon bridge. Crystal structures of HMo(CO)(2) [eta(5):eta(1)-C5H4(CH2)(2)PR2] with all three R groups (R = Ph, Cy, and tBu) are reported. Syntheses of the C-3-bridged complex, HMo(CO)(2) [eta(5):eta(1)-C4H5(CH2)(3)-PPh2], and a W analogue, HW(CO)(3) [eta(5)-C5H4(CH2)(2)(PBu2)-Bu-t], were carried out by analogous routes. Hydride transfer to Ph3C+BAr'(-)(4) [Ar' = 3,5-bis(trifluoromethyl)phenyl] from the catalyst precursors HMo(CO)(2) [eta(5):eta(1)-C5H4(CH2)(2)PR2] leads to homogeneous catalysts for hydrogenation of ketones, with the best performance being found for R = Cy. Protonation of HMo(CO)(2)[eta(5):eta(1)-C5H4(CH2)(2)PR2], by HOTf leads to metal triflate complexes (TfO)MO(CO)(2)[eta(5):eta(1)-C5H4(CH2)(2)PR2], which are used in ketone hydrogenation. Compared to the previously prepared complexes that did not have the phosphine and Cp linked together, these new complexes provide catalysts that have much longer lifetimes (up to about 500 turnovers) and higher thermal stability. Solvent-free ketone hydrogenation can be carried out with these complexes at catalyst loadings as low as 0.1 mol %.

  DOI：

  10.1021/om050564h