Os3(CO)9(μ-C4Ph4) | 34766-74-0

• 英文名称: Os3(CO)9(μ-C4Ph4)
• 英文别名: [Os3(CO)9(μ-C4Ph4)]
• CAS: 34766-74-0
• 化学式: C₃₇H₂₀O₉Os₃
• 分子量: 1179.16
• InChiKey: WSCYTIANMSVGRL-UHFFFAOYSA-N

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：

  Os3(CO)9(μ-C4Ph4) 在 一氧化碳 作用下， 以 萘烷 为溶剂， 生成
  参考文献：
  名称：

  Kinetics of reaction of dodecacarbonyltriosmium with diphenylacetylene

  摘要：

  DOI：

  10.1021/ja00278a015
• 作为产物：
  描述：

  以 not given 为溶剂， 生成 Os3(CO)8(μ-H)(μ-PhCCPhCPhCC6H4) 、 Os3(CO)9(μ-C4Ph4)
  参考文献：
  名称：

  The photochemical and thermal reactions of a triosmium cluster carrying a γ-pyrone ligand with alkynes

  摘要：

  The reaction of the cluster Os-3(CO)(10)(mu-H)(mu-gamma-C5H3O2) (1) with a number of alkynes under thermal or visible light irradiation conditions, afforded in most cases the dinuclear complexes Os-2 (CO)(6)(mu-gamma-C5H3O2)(mu-LH) (L = PhCCPh, (BuCCH)-Bu-l, (BuCCMe)-Bu-l or EtCCEt) (2) or the trinuclear chain complexes Os-3(CO)(9)(mu-H)(mu-gamma-C5H3O2)(mu-RCCHC6H4) (R = H, Ph) (3). In the case of PhCCPh, a new isomer of Os-3(CO)(8)(PhCCPh)(2), viz., Os-3(CO)(8)(mu-PhCCPh)(mu-PhCCHC6H4) (7) has been isolated and characterised. (C) 2003 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2003.09.022

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。
• Complex Kinetics of “Simple” Substitution Reactions of Os₃(CO)₉(μ-C₄Ph₄) with Smaller P-Donor Nucleophiles
  作者：Anthony J. Poë、Consuelo Moreno

  DOI：10.1021/om9906464

  日期：1999.12.1

  reactivity toward adduct formation is very high, only high nuclearity clusters that contain encapsulated C atoms being known to react faster. Nucleophiles with θ ≤ 120 ± 4° react at rates that are independent of their size and that increase substantially with their σ-basicity. When the cone angles are larger, steric retardation is observed. Equilibrium constants for adduct formation by 14 of the nucleophiles

  在三角OS中OSmacyclopentadiene环3簇锇3（CO）9（μ-C 4博士4）桥接两个O的原子的并且被发现以激活在第三OS原子缔发作（其是在OS（CO）与母簇OS 3（CO）12的反应相比，它的4部分）的分解系数约为10 9。在庚烷中的总体反应的17 P-供体亲核体与托尔曼锥角θ ≤143°导致在该OS（CO）取代4集中在三个快速但从动力学上可观察到的阶段：（i）亲核试剂可逆地攻击以形成加合物，其中簇中的OS-OS键已被破坏，（ii）CO的损失和新的封闭OS 3簇的形成通常，（iii）最初形成的簇的异构化以形成最终的取代产物。速率对亲核试剂的σ碱性和大小的依赖性表明，对加合物形成的标准反应性非常高，只有包含被封装的C原子的高核簇才能更快地反应。θ的亲核体≤120±4°的反应速率与其大小无关，并且随其σ碱度而显着增加。当锥角较大时，观察到空间延迟。从该OS加成物形成和L的损失的速
• Reactivity of electron-deficient triosmium quinoline cluster [Os3(CO)9(μ3-η2-C9H6N)(μ-H)] with alkynes
  作者：Shishir Ghosh、Md. Rafique Al-Mamun、G.M. Golzar Hossain、Shariff E. Kabir

  DOI：10.1016/j.ica.2011.08.023

  日期：2011.11

  triosmium cluster [Os 3 (CO) 9 (μ 3 -η 2 -C 9 H 6 N)(μ-H)] ( 1 ) with various alkynes are described. Cluster 1 readily reacts with the activated alkyne dimethyl acetylenedicarboxylate (dmad) upon mild heating (65–70 °C) to give the adduct [Os 3 (CO) 9 (μ-C 9 H 6 N)(μ 3 -MeO 2 CCCHCO 2 Me)] ( 2 ). In contrast, a similar reaction of 1 with diphenylacetylene affords previously reported compounds [Os 3 (CO)

  摘要描述了缺电子的cluster簇[Os 3（CO）9（μ3-η2 -C 9 H 6 N）（μ-H）]（1）与各种炔烃的反应。轻度加热（65–70°C）时，簇1容易与活化的炔炔二甲基二甲基炔烃（dmad）反应，生成加合物[Os 3（CO）9（μ-C9 H 6 N）（μ3 -MeO 2 CCCHCO 2 Me）]（2）。相反，1与二苯乙炔的类似反应可得到先前报道的化合物[Os 3（CO）10（μ-η2 -C 9 H 6 N）（μ-H）]（3），[Os 3（CO）9 （μ-C4 Ph 4）]（4）和[Os 3（CO）8 μ3 -C（C 6 H 4）C 3 Ph 3}（μ-H）]（5）和2-丁炔仅得到已知化合物[Os 3（CO）7（μ-C4 Me 4）（μ3 -C 2 Me 2）]（6）。新的簇2的特征在于结合了光谱数据和单晶X射线衍射分析。
• Steric limitations in associative substitution reactions of Os3(CO)9(μ-C4Ph4)
  作者：Anthony J. Poë、David H. Farrar、Ravindranath Ramachandran、Consuelo Moreno

  DOI：10.1016/s0020-1693(97)05992-6

  日期：1998.6

  Reactions of the cluster Os-3(CO)(9)(mu-C4Ph4) (I) with a large number of smaller P-donor nucleophiles (Tolman cone angle theta less than or equal to 143 degrees) proceed rapidly in heptane at room temperature via associative adduct formation to form the monosubstituted products. However, reactions with several larger P-donor nucleophiles (theta greater than or equal to 145 degrees) in heptane at room temperature yield, in a single observable bimolecular step, a mixture of mononuclear and dinuclear products and it is therefore not possible to synthesize the monosubstituted clusters directly with these larger ligands. Crystallographic structures of Os-3(CO)(8)(etpb)(mu-C4Ph4).(CH3OH) (2etpb) (etpb = P(OCH2)(3)CEt) and Os-3(CO)(8)(P(OPh)3)(mu-C4Ph4).(C6H14) (2P(OPh)(3)) have been determined and show that the substituent has displaced a CO ligand from the Os(CO)(4) moiety in 1. (C) 1998 Elsevier Science S.A. All rights reserved.