(μ-H)HOs3(CO)10(P(OPh)3) | 82456-55-1

• 英文名称: (μ-H)HOs3(CO)10(P(OPh)3)
• 英文别名: H(μ-H)Os3(CO)10(P(OPh)3)
• CAS: 82456-55-1；209978-77-8
• 化学式: C₂₈H₁₇O₁₃Os₃P
• 分子量: 1163.01
• InChiKey: NUYDWQORFBEFEO-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：

  (μ-H)HOs3(CO)10(P(OPh)3) 以 further solvent(s) 为溶剂， 生成 (μ-H)2Os3(CO)9(P(OPh)3)
  参考文献：
  名称：

  Systematic CO dissociation kinetics of (μ2-H)(H)Os3(CO)10L, clusters (L = P-donor ligands)

  摘要：

  The kinetics of decarbonylation of (mu(2)-H)(H)Os-3(CO)(10)L (L = P(OPh)(3), P(OCH2)(3)CEt, PPh3, P-o-tol(3), PEt3, PCy3, P-t-Bu-3) to form (mu(2)-H)(2)Os-3(CO)(9)L in paraffin hydrocarbons have been studied over a range of temperatures. Rates are similar to 10(5) times faster than CO dissociation rates of analogous Os-3(CO)(11)L clusters but no appreciable kinetic isotope effect is observed at 60 degrees C when L = PPh3. Rates decrease with increasing net electron donor ability of the ligands L according to the equation log k=alpha(L)+beta(L) delta((CO)-C-13) (beta(L)=0.09+/-0.02 and 0.11+/-0.03 ppm(-1) at 50 and 100 degrees C, respectively), only the largest substituent P-t-Bu-3 (Tolman cone angle 182 degrees) showing an enhanced rate due to steric effects, The absence of any detectable steric effects when the cone angles of the substituents are less than or equal to 170 degrees is attributed to a close balance between the opposing effects of Os-CO bond breaking and the contraction of the hydride-bridged Os-Os bond. This picture is supported by generally small or negative values of Delta S-not equal. These electronic and steric effects are quite small, the largest difference in rates corresponding to only similar to 4% of the average value of Delta G(not equal), However, this is due to a change of similar to 4 kcal mol(-1) in Delta H-not equal that is almost balanced by a change in T Delta S-not equal. It is the energy provided by strengthening the bonding in the hydride-bridged Os-Os region of the cluster that largely compensates for the energy needed to break the Os-CO bond and that leads to the greatly enhanced rates for these hydride clusters. Reactions of (mu(2)-H)(2)Os-3(CO)(9)L with other P-donor ligands L' appear likely to lead to adducts (mu(2)-H)HOs3(CO)(9)LL' in which both P-donor ligands are attached to the same Os atom in a way that allows for isomerism depending on whether L' is added to (mu 2-H)(2)Os-3(CO)(9)L or L to (mu(2)-H)(2)Os-3(CO)(9)L'.

  DOI：

  10.1016/s0020-1693(97)05466-2
• 作为产物：
  描述：

  亚磷酸三苯酯 、 Os3(μ-H)2(CO)10 以 正庚烷 、 二氯甲烷 为溶剂， 以99%的产率得到(μ-H)HOs3(CO)10(P(OPh)3)
  参考文献：
  名称：

  Systematic CO dissociation kinetics of (μ2-H)(H)Os3(CO)10L, clusters (L = P-donor ligands)

  摘要：

  The kinetics of decarbonylation of (mu(2)-H)(H)Os-3(CO)(10)L (L = P(OPh)(3), P(OCH2)(3)CEt, PPh3, P-o-tol(3), PEt3, PCy3, P-t-Bu-3) to form (mu(2)-H)(2)Os-3(CO)(9)L in paraffin hydrocarbons have been studied over a range of temperatures. Rates are similar to 10(5) times faster than CO dissociation rates of analogous Os-3(CO)(11)L clusters but no appreciable kinetic isotope effect is observed at 60 degrees C when L = PPh3. Rates decrease with increasing net electron donor ability of the ligands L according to the equation log k=alpha(L)+beta(L) delta((CO)-C-13) (beta(L)=0.09+/-0.02 and 0.11+/-0.03 ppm(-1) at 50 and 100 degrees C, respectively), only the largest substituent P-t-Bu-3 (Tolman cone angle 182 degrees) showing an enhanced rate due to steric effects, The absence of any detectable steric effects when the cone angles of the substituents are less than or equal to 170 degrees is attributed to a close balance between the opposing effects of Os-CO bond breaking and the contraction of the hydride-bridged Os-Os bond. This picture is supported by generally small or negative values of Delta S-not equal. These electronic and steric effects are quite small, the largest difference in rates corresponding to only similar to 4% of the average value of Delta G(not equal), However, this is due to a change of similar to 4 kcal mol(-1) in Delta H-not equal that is almost balanced by a change in T Delta S-not equal. It is the energy provided by strengthening the bonding in the hydride-bridged Os-Os region of the cluster that largely compensates for the energy needed to break the Os-CO bond and that leads to the greatly enhanced rates for these hydride clusters. Reactions of (mu(2)-H)(2)Os-3(CO)(9)L with other P-donor ligands L' appear likely to lead to adducts (mu(2)-H)HOs3(CO)(9)LL' in which both P-donor ligands are attached to the same Os atom in a way that allows for isomerism depending on whether L' is added to (mu 2-H)(2)Os-3(CO)(9)L or L to (mu(2)-H)(2)Os-3(CO)(9)L'.

  DOI：

  10.1016/s0020-1693(97)05466-2

文献信息

• NMR characterization of four new isomers of H(μ-H)Os3(CO)10(phosphine)
  作者：Silvio Aime、Roberto Gobetto、Esteve Valls

  DOI：10.1016/s0020-1693(98)00150-9

  日期：1998.7