[Cp*Mo(H)(MeCN)2(dppe)](2+) | 188550-32-5

• 英文名称: [Cp*Mo(H)(MeCN)2(dppe)](2+)
• 英文别名: Cp*Mo(dppe)H(MeCN)2(2+)
• CAS: 188550-32-5；177342-87-9
• 化学式: C₄₀H₄₆MoN₂P₂
• 分子量: 712.706
• InChiKey: QNRBTHSXRZYIMC-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：

  [Cp*Mo(H)3(dppe)](+) 、 乙腈 以 乙腈 为溶剂， 生成 [Cp*Mo(H)(MeCN)2(dppe)](2+)
  参考文献：
  名称：

  Electrochemical and DFT studies of the oxidative decomposition of the trihydride complexes Cp*M(dppe)H3 (M = Mo, W) in acetonitrile

  摘要：

  A detailed electrochemical study of the oxidative decomposition of the trihydride complexes Cp*M(dppe)H3 (M = Mo, W) in acetonitrile is presented. For the Mo complex, the decomposition occurs by four different pathways involving classical and non-classical tautomers, whereas only the classical form is accessible for the W derivative. Each of the decomposition pathways has been quantitatively assessed by analyses of the linear sweep voltammograms. In addition to the previously established (B. Pleune, D. Morales, R. Meunier-Prest, P. Richard, E. Collange, J. C. Fettinger and R. Poli, J. Am. Chem. Soc., 1999, 121, 2209–2225) deprotonation, disproportionation, and H2 reductive elimination occurring via the non-classical tautomer of the 17-electron complex [Cp*Mo(dppe)H3]+ (obtained by oxidation at E1/2 = −0.33 V vs. Ag/AgCl), a new decomposition pathway from the more stable classical tautomer has been identified following a second oxidation process. In addition, the oxidatively induced H2 reductive elimination, previously evidenced only in THF or CH2Cl2, has been quantitatively assessed in MeCN. This process occurs preferentially by an associative mechanism (k = 0.020(4) M−1s−1) via the 19-electron [Cp*Mo(dppe)H(H2)(MeCN)]+ intermediate and is therefore in direct competition with the disproportionation mechanism. The resulting 17-electron [Cp*Mo(dppe)H(MeCN)]+ product is further oxidized at ca. 0.2 V. The oxidation of [Cp*Mo(dppe)H3]+ occurs at ca. 1.0 V and the resulting 16-electron [Cp*Mo(dppe)H3]2+ complex immediately delivers a proton to the starting material, giving [Cp*Mo(dppe)H4]+ and [Cp*Mo(dppe)H2]+. The latter coordinates MeCN in a rate determining step to afford [Cp*Mo(dppe)H2(MeCN)]+. The mechanistic details are consistent with studies at different scan rates and different MeCN concentrations, and are backed up by DFT calculations.

  DOI：

  10.1039/b518343j

文献信息

• Stable Paramagnetic Half-Sandwich Mo(V) and W(V) Polyhydride Complexes. Structural, Spectroscopic, Electrochemical, Theoretical, and Decomposition Mechanism Studies of [Cp*MH₃(dppe)]⁺ (M = Mo, W)
  作者：Brett Pleune、Dolores Morales、Rita Meunier-Prest、Philippe Richard、Edmond Collange、James C. Fettinger、Rinaldo Poli

  DOI：10.1021/ja9834881

  日期：1999.3.1

  Compounds Cp*MHsub 3}(dppe) (M = Mo, 1; W, 2) are oxidized chemically and electrochemically to the corresponding 17-electron cations 1sup +} and 2sup +}. Analogous oxidations of 1-dsub 3} and 2-dsub 3} provide 1sup +}-dsub 3} and 2sup +}-dsub 3}, respectively. Complex 2sup +} is stable in CHsub 2}Clsub 2}, THF and MeCN at room temperature. A single-crystal X-ray analysis of the PFsub 6}sup

  化合物 Cp*MHsub 3}(dppe) (M = Mo, 1; W, 2) 被化学和电化学氧化成相应的 17 个电子阳离子 1sup +} 和 2sup +}。1-dsub 3} 和 2-dsub 3} 的类似氧化分别提供 1sup +}-dsub 3} 和 2sup +}-dsub 3}。配合物 2sup +} 在室温下在 CHsub 2}Clsub 2}、THF 和 MeCN 中是稳定的。PFsub 6}sup minus}} salt of 2sup +} 的单晶 X 射线分析显示 [CpWHsub 3}(PHsub 2}CHsub 2 }CHsub 2}PHsub 2})]sup +} 模型在 B3LYP/LANL2DZ 级别。中性类似物的相同计算也再现了先前报道的 1 的三角棱柱结构。 Mo 和 W 化合物在氧化时 MH 伸缩振动的蓝移表明