[RuHCl(CO)((t)Bu2P(CH2)5PBu(t)2]2 | 477338-72-0

• 英文名称: [RuHCl(CO)((t)Bu2P(CH2)5PBu(t)2]2
• CAS: 477338-72-0
• 化学式: C₄₄H₉₄Cl₂O₂P₄Ru₂
• 分子量: 1052.17
• InChiKey: FXWXYAZLMFLEFC-UHFFFAOYSA-L

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：

  dichloro(1,5-cyclooctadiene)ruthenium(II) 、 1,5-二(二叔丁基膦)戊烷 在 NEt₃ 作用下， 以 further solvent(s) 为溶剂， 以84%的产率得到[RuHCl(CO)((t)Bu2P(CH2)5PBu(t)2]2
  参考文献：
  名称：

  Experimental and Computational Study of Pincer Complexes of Ruthenium with Py, CO, and N₂ Ligands

  摘要：

  Addition of pyridine to the syn and anti isomers of cis-RuHCl[(Bu2PCH2CH2)-Bu-t((E)-CH=CH)CH2PBu2t] (1) afforded a single isomer of trans,cis,anti-RuHCl(Py)[(Bu2PCH2CH2)-Bu-t((E)-CH=CH)CH2PBu2] (2), where the anti alpha-HC-RuH configuration was established by a difference NOE experiment. The carbonyl complex RuCl(CO)[CH(C2H4PBu2t)(2)] (3) was obtained from 2 under CO, and two hydride complexes, RuH(CO)[CH(C2H4PBu2)(2)] (4) and RuH(N-2)[CH(C2H4PBu2t)(2)] (5), were prepared from 3 and 1, respectively, using Li[HBEt3] as the hydride source. Decarbonylation of isoamyl alcohol with polymeric [RuCl2(COD)],, in the presence of 1,5-bis(di-tert-butylphosphino)pentane ((DBPP)-B-t) resulted in isolation of the 16-atom-ring binuclear species [RuHCl(CO)((DBPP)-B-t)](2) (6). New products 3-5 were characterized by single-crystal X-ray analysis. In the computational study, we successfully modeled complexes 1-4 using the ONIOM methodology. It was established that the bulky PBu2t groups are responsible for the electronically unfavorable cis arrangement of the CO and Cl ligands in 3. B3PW91 calculations of the transition state structures for the intramolecular olefin insertion into the Ru-H bond in anti-1, trans, cis-2, and cis, trans-2 gave barrier heights of 28.3, 27.1, and 17.7 kcal/mol, respectively.

  DOI：

  10.1021/om0205142