HRu(CO)(PMe3)(NCCD3)3(1+) | 136947-52-9

• 英文名称: HRu(CO)(PMe3)(NCCD3)3(1+)
• CAS: 136947-52-9
• 化学式: C₁₀H₁₉N₃OPRu
• 分子量: 338.253
• InChiKey: RGWCMWJMUOXDQE-STWCLVJWSA-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：

  四氟硼酸-二乙醚络合物 、 C5H5Ru(CO)(PMe3)H 以 氘代乙腈 为溶剂， 生成 C5H5Ru(CO)(PMe3)(NCCD3)(1+) 、 HRu(CO)(PMe3)(NCCD3)3(1+)
  参考文献：
  名称：

  Oxidation of CpRu(CO)(PMe3)H by 2/3, 1, and 2 electrons by the judicious choice of reaction conditions. Generation of a bridging hydride via the reaction between a 17-electron metal hydride cation radical and its conjugate base

  摘要：

  The hydride complex CpRu(CO)(PMe3)H (1) undergoes a chemically irreversible oxidation at 0.34 V vs the ferrocene/ferrocenium couple. By the judicious choice of reaction conditions, the oxidation of 1 in acetonitrile may be directed toward a 2/3-, 1-, or 2-electron process. The room temperature oxidation of 1 with Cp2Fe+PF6- in acetonitrile-d3 leads to the virtually quantitative (by H-1 NMR) generation of [CpRu(CO)(PMe3)]2(mu-H)+ (5), HRu(CO)(PMe3)(NCCD3)3+ (4-d9), and cyclopentadiene in a 1:1:1 molar ratio, in accord with an overall 2/3-electron oxidation of 1. A trace of CpRu(CO)(PMe3)(NCCD3)+ (2-d3) was also observed. Dihydrogen complex CpRu(CO)(PMe3)(eta-2-H-2)+ (3) was observed as an intermediate in the reaction, and it reacted to form 4-d9 and cyclopentadiene. Ferrocenium oxidation of 1 in the presence of 2,6-lutidine proceeded as a 1-electron process, yielding 5 and H+. In the presence of pyrrolidine, a 2-electron process ensued and resulted in the formation of 2-d3 and H+. Coulometry and preparative-scale experiments performed in acetonitrile proceeded somewhat differently. The electrochemical oxidation was a 1-electron process in the absence of base, yielding mostly 2 and 4, whereas a 2-electron process took place in the presence of 2,6-lutidine or pyrrolidine, yielding 2. The key to explaining all of the results is that an initial proton-transfer reaction from 1.+ to a base occurs. This transfer may take place rapidly from 1.+ to pyrrolidine, but only slowly to 2,6-lutidine. Proton transfer from 1.+ to the base yields the radical CpRu(CO)(PMe3).. The latter results in the formation of 5 via combination with 1.+ when 1.+ concentrations are relatively high. This is the case when 1 or 2,6-lutidine functions as a base. Otherwise, a second oxidation of CpRu(CO)(PMe3). produces 2. Pyrrolidine effects the rapid deprotonation of the cation radical, effectively depleting the solution of 1.+ and closing the pathway leading to 5.

  DOI：

  10.1021/ja00025a020