Os(CO)3(PCy3)2 | 139943-37-6

• 英文名称: Os(CO)3(PCy3)2
• CAS: 139943-37-6
• 化学式: C₃₉H₆₆O₃OsP₂
• 分子量: 835.099
• InChiKey: ZBHKDHNXLIUVBT-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 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

• 作为反应物：
  描述：

  Os(CO)3(PCy3)2 、 四丁基氯化铵 在 (C₄H₉)4NPF₆ 作用下， 以 二氯甲烷 为溶剂， 生成
  参考文献：
  名称：

  Song, Lin; Trogler, William C., Journal of the American Chemical Society, 1992, vol. 114, # 9, p. 3355 - 3361

  摘要：

  DOI：
• 作为产物：
  描述：

  三环己基膦 在 CO 、 potassium graphite (C₈K) 作用下， 以 四氢呋喃 为溶剂， 生成 Os(CO)3(PCy3)2
  参考文献：
  名称：

  Song, Lin; Trogler, William C., Journal of the American Chemical Society, 1992, vol. 114, # 9, p. 3355 - 3361

  摘要：

  DOI：

文献信息

• Electronic and steric effects in fragmentation reactions of Os₃(CO)₉(μ-C₄Ph₄)
  作者：Kevin A. Bunten、Consuelo Moreno、Anthony J. Poë

  DOI：10.1039/b418940j

  日期：——

  P-Donor nucleophiles of cone angle ≥145° are known to react with Os3(CO)9(μ-C4Ph4) quite differently from those with cone angles ≤143°. A detailed and systematic kinetic study of the rather slow kinetics of reactions with 11 of the larger nucleophiles is described, and the results are analysed according to standard QALE protocols. (QALE = quantitative analysis of ligand effects). The results are compared with those previously reported for 17 of the smaller phosphines, which react much more rapidly. The pronounced difference in behaviour between these two groups of nucleophiles is ascribable to major differences between the ease of formation of different intermediate Os3(CO)9L(μ-C4Ph4) adducts. The cluster is proposed to be capable of opening up to form a nido structure that has a small, well defined opening capable of accommodating any of the smaller nucleophiles quite easily. However, this opened nido structure is concluded to be extremely rigid and incapable of further opening to accommodate any of the larger nucleophiles. These have to take advantage of an alternative nido structure that contains a much larger opening but that requires considerably more energy for it to be formed. These results are compared with those for the clusters M5C(CO)15 (M = Ru or Fe), which show somewhat similar behaviour. This is ascribed to the complexity of the structures of the clusters that allows them to form alternative nido structures of the sort described, something that more symmetrical clusters are apparently incapable of doing.

  已知锥角≥145°的P给体亲核试剂与Os3(CO)9(μ-C4Ph4)的反应方式与锥角≤143°的亲核试剂截然不同。本文详细系统地研究了11种较大亲核试剂与Os3(CO)9(μ-C4Ph4)反应的缓慢动力学过程，并按照标准QALE协议分析了结果（QALE=配体效应的定量分析）。结果与之前报道的17种较小膦类亲核试剂的反应结果进行比较，后者反应速度快得多。这两组亲核试剂行为上的显著差异可归因于不同中间体Os3(CO)9L(μ-C4Ph4)络合物形成难易程度的主要差异。提出的簇合物能够打开形成一种具有小而明确开口的巢型结构，可以很容易地容纳任意一种较小的亲核试剂。然而，这种打开的巢型结构被认为是极其刚性的，无法进一步打开以容纳任何较大的亲核试剂。这些较大的亲核试剂必须利用一种开口大得多的替代巢型结构，但形成该结构需要更多的能量。这些结果与M5C(CO)15簇合物（M=Ru或Fe）的结果进行了比较，后者表现出类似的行为。这归因于簇合物结构的复杂性，使得它们能够形成上述替代的巢型结构，而通常对称性更高的簇合物则显然无法做到这一点。