[Nb(η5-C5H4SiMe3)2(κ2-O-O'-O2CCH2CH2COOMe)] | 1383936-42-2

• 英文名称: [Nb(η5-C5H4SiMe3)2(κ2-O-O'-O2CCH2CH2COOMe)]
• CAS: 1383936-42-2
• 化学式: C₂₁H₃₃NbO₄Si₂
• 分子量: 498.568
• InChiKey: BWYFCOYZDRPYOO-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  一氧化碳 、 [Nb(η5-C5H4SiMe3)2(κ2-O-O'-O2CCH2CH2COOMe)] 以 四氢呋喃 为溶剂， 生成 [Nb(η5-C5H4SiMe3)2(κ1-O-O2CCH2CH2COOMe)(CO)]
  参考文献：
  名称：

  Experimental and Theoretical Studies of the Hydrogenation of α,β-Unsaturated Acids by an 18e Hydride Carbonylniobocene Complex

  摘要：

  The reaction of the niobocene complex [Nb(eta(5)-C5H4SiMe3)(2)(H)(CO)] (1) with alpha,beta-unsaturated acids, namely, fumaric and maleic acids, and methylfumarate ester yielded the corresponding carboxylato-containing niobocene derivatives [Nb(eta(5)-C5H4SiMe3)(2)(kappa(1)-O-OOC-CH2-CH2-R)(CO)] (R = COOH (2); R = COOMe (3)), resulting from the hydrogenation of the C=C bond and the consequent coordination of a carboxylato moiety on the Nb center. The process represents the first reported example of the hydrogenation of alpha,beta-unsaturated acids mediated by a hydride niobocene complex. Spectroscopic and theoretical studies at the DFT level have allowed for proposing a plausible reaction mechanism. Initial coordination of the C=C bond to the Nb center is followed by the insertion of this bond into the Nb-H bond, and the reaction is completed by a proton transfer from the carboxylic moiety to the alpha-carbon of the alkyl moiety, giving rise to the final kappa(1)-carboxylato ligand.

  DOI：

  10.1021/om300510m
• 作为产物：
  描述：

  [Nb(η5-C5H4SiMe3)2(κ1-O-O2CCH2CH2COOMe)(CO)] 以 四氢呋喃 为溶剂， 以95%的产率得到[Nb(η5-C5H4SiMe3)2(κ2-O-O'-O2CCH2CH2COOMe)]
  参考文献：
  名称：

  Experimental and Theoretical Studies of the Hydrogenation of α,β-Unsaturated Acids by an 18e Hydride Carbonylniobocene Complex

  摘要：

  The reaction of the niobocene complex [Nb(eta(5)-C5H4SiMe3)(2)(H)(CO)] (1) with alpha,beta-unsaturated acids, namely, fumaric and maleic acids, and methylfumarate ester yielded the corresponding carboxylato-containing niobocene derivatives [Nb(eta(5)-C5H4SiMe3)(2)(kappa(1)-O-OOC-CH2-CH2-R)(CO)] (R = COOH (2); R = COOMe (3)), resulting from the hydrogenation of the C=C bond and the consequent coordination of a carboxylato moiety on the Nb center. The process represents the first reported example of the hydrogenation of alpha,beta-unsaturated acids mediated by a hydride niobocene complex. Spectroscopic and theoretical studies at the DFT level have allowed for proposing a plausible reaction mechanism. Initial coordination of the C=C bond to the Nb center is followed by the insertion of this bond into the Nb-H bond, and the reaction is completed by a proton transfer from the carboxylic moiety to the alpha-carbon of the alkyl moiety, giving rise to the final kappa(1)-carboxylato ligand.

  DOI：

  10.1021/om300510m