OsH3Cl(P(tert-butyl)2(methyl))2 | 393088-93-2

• 分子结构分类: 有机化合物 - 有机磷化合物 - 有机膦及其衍生物
• 英文名称: OsH3Cl(P(tert-butyl)2(methyl))2
• 英文别名: chloro(trihydrido)osmium;ditert-butyl(methyl)phosphane
• CAS: 393088-93-2
• 化学式: C₁₈H₄₅ClOsP₂
• 分子量: 549.156
• InChiKey: FZEUVLCKDVTDBT-UHFFFAOYSA-M

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：

  OsH3Cl(P(tert-butyl)2(methyl))2 以 甲苯 为溶剂， 生成
  参考文献：
  名称：

  通过Ru或Os容易地进行C（sp（2））/ OR键裂解。

  摘要：

  Os（H）（3）ClL（2）（L = P（i）Pr（3）或P（t）Bu（2）Me）显示为对“ OsHClL（2）”有用的“前体”与乙烯基醚反应，首先形成eta（2）-烯烃加合物，然后异构化为羧甲基OsHCl [CMe（OR）] L（2）。随后的R和L依赖的反应涉及C（sp（2））-OR键的裂解，使卡宾或亚乙烯基络合物。探索了这些反应的机理，并基于DFT（B3PW91）计算，讨论了Ru与Os的热力学差异以及OR基团和旁观者膦配体的影响。

  DOI：

  10.1021/ic010729o
• 作为产物：
  描述：

  ditert-butyl(methyl)phosphane;dichloro(dihydrido)osmium 、 氢气 在 Et₃N 作用下， 以 甲苯 为溶剂， 以75%的产率得到OsH3Cl(P(tert-butyl)2(methyl))2
  参考文献：
  名称：

  Isomeric Hydrido/Vinylidene, MH(halide)(CCH₂)L₂, and Ethylidyne, M(halide)(C−CH₃)L₂ (M = Os, Ru; L = Phosphine), Are Energetically Similar but Not Interconverting

  摘要：

  It is shown that there is no deuterium-isotope incorporation in the vinylidene CHPh group of RuDX(CCHPh)((PBu2Me)-Bu-t)(2) (X = Cl, I) on the time scale of 24 h at 25 degrees C, which indicates that the (unobserved) isomeric alkylidyne species RuX(CCHDPh)((PBu2Me)-Bu-t)(2) is not readily accessible under these conditions. Ab initio (B3LYP) calculations on the model MHCl(CCH2)(PH3)(2) (M = OS, Ru) show the ethylidyne isomer MCl(CCH3)(PH3)(2) to be close in energy (2.5, -1.1 kcal mol(-1) for Os and Ru, respectively) and effectively inaccessible at 25 degrees C due to the high energy (54.2, 45.5 kcal mol(-1) for Os and Ru, respectively) of the transition state for such a 1,3-migration. In contrast, simple rotation of the CCH2 group of MHCl(CCH2)(PH3)(2) by 180 degrees around the C-C axis is calculated to have a low barrier (8.1, 4.3 kcal mol(-1) for Os and Ru, respectively), indicating this to be the mechanism for isomerization observed in OsHCl(CCHPh)((PPr3)-Pr-i)(2).

  DOI：

  10.1021/om9709493

文献信息

• Facile C(sp²)/O₂CR bond cleavage by Ru or Os
  作者：German Ferrando、Joseph N. Coalter, III、Hélène Gérard、Dejian Huang、Odile Eisenstein、Kenneth G. Caulton

  DOI：10.1039/b306111f

  日期：——

  [RuHClL2]2, L = PiPr3, reacts with H2CCH(O2CR) (R = CH3, CF3, C6H5) during mixing at 20 °C, via two observable intermediates, to give RuCl(O2CR)(CHMe)L2; this carbene complex then redistributes the Cl and O2CR groups. Vinyl tosylate gives RuCl(OTs)(CHMe)L2 already at −60 °C. Vinyl chloroformate, H2CCH(O2CCl) reacts rapidly with [RuHClL2]2 to give the olefin metathesis catalyst RuCl2(CHMe)L2 and CO2. Os(H)3ClL2 (L = PiPr3 or PtBu2Me) reacts with vinyl esters H2CCHE (E = O2CR) to form first an η2-olefin adduct. This is followed by C/O bond cleavage, giving the carbyne OsHCl(O2CCF3)(CMe)L2. Vinyl chloroformate and Os(H)3ClL2 gives OsHCl2(CMe)L2 and CO2. RuHCl(PPh3)3 reacts with vinyl chloroformate, via RuCl(O2CCl)(CHMe)(PPh3)2, to give RuCl2(CHMe)(PPh3)2 while OsHCl(PPh3)3 reacts analogously, through observable OsCl2(CHMe)(PPh3)2, to form OsHCl2(CMe)(PPh3)2. Vinyl trifluoroacetate converts OsHCl(PPh3)3, to OsHCl(O2CCF3)(CMe)(PPh3)2. The less π-basic metal in OsH(CO)(PtBu2Me)2+ reacts with vinyl esters to give only an olefin adduct; detectable binding of the ester oxygen to Os in this adduct suggests a mechanism for carboxylate migration from carbene carbon to metal. The mechanisms of these reactions are explored, and the thermodynamic disparity between Ru and Os is discussed. DFT (B3PW91) calculations have been carried out to establish the energy pattern of possible products. The thermodynamic preference for cleaving the C–O2CR bond is shown to have a thermodynamic origin associated with the energy of the formed Ru–O2CR bond. The calculations also indicate the very large thermodynamic driving force for loss of CO2 in the case of H2CCH(O2CCl). The corresponding loss of CO2 is shown to be thermodynamically unfavorable in the case of H2CCH(O2CR). The energy of the Ru-R bond is a key factor.

  [RuHClL2]2，L = PiPr3，在 20 °C下与 H2CCH(O2CR)（R = CH3、CF3、C6H5）发生反应，通过两个可观察到的中间产物，得到 RuCl(O2CR)(CHMe)L2；这个碳烯络合物随后重新分配了 Cl 和 O2CR 基团。对甲苯磺酸乙烯酯在-60 °C时就能得到 RuCl(OTs)(CHMe)L2。氯甲酸乙烯酯 H2CCH(O2CCl) 与 [RuHClL2]2 快速反应，生成烯烃偏聚催化剂 RuCL2(CHMe)L2 和 CO2。Os(H)3ClL2（L = PiPr3 或 PtBu2Me）与乙烯基酯 H2CCHE（E = O2CR）反应，首先生成η2-烯烃加合物。随后，C/O 键发生裂解，生成邻碳化合物 OsHCl(O2C )(CMe)L2。氯甲酸乙烯酯和 Os(H)3ClL2 生成 OsHCL2(CMe)L2 和 。RuHCl(PPh3)3 通过 RuCl(O2CCl)(CHMe)(PPh3)2 与氯甲酸乙烯酯反应，生成 RuCL2(CHMe)(PPh3)2，而 OsHCl(PPh3)3 通过可观察到的 OsCL2(CHMe)(PPh3)2，发生类似反应，生成 OsHCL2(CMe)(PPh3)2。三氟乙酸乙烯酯将 OsHCl(PPh3)3 转化为 OsHCl(O2C )(CMe)(PPh3)2。OsH(CO)(PtBu2Me)2+中π基含量较低的金属与乙烯基酯发生反应，只生成一种烯烃加合物；在这种加合物中可检测到酯氧与 Os 的结合，这表明羧基从碳到金属的迁移机制。本文探讨了这些反应的机理，并讨论了 Ru 和 Os 之间的热力学差异。通过 DFT（B3PW91）计算，确定了可能产物的能量模式。结果表明，裂解 C-O2CR 键的热力学偏好与所形成的 Ru-O2CR 键的能量有关。计算还表明，在 H2CCH(O2CCl) 的情况下，二氧化碳损失的热力学驱动力非常大。在 H2CCH(O2CR) 的情况下，相应的 损失在热力学上是不利的。Ru-R 键的能量是一个关键因素。
• New Access to Vinylidenes from Ruthenium Polyhydrides
  作者：Montserrat Oliván、Odile Eisenstein、Kenneth G. Caulton

  DOI：10.1021/om970095m

  日期：1997.5.1

  with RuH3XL2 (X = Cl, I; L = PtBu2Me) occurs (in the time of mixing) in a 2:1 stoichiometry to release RHCCH2 and form the vinylidene complexes RuHX(CCHR)L2. Ab initio DFT (B3LYP) calculations show that the vinylidene complex has a Y structure with a Cl at the foot of the Y. No intermediate is seen for this reaction, even at low temperature, or for the analogous reaction of OsH3Cl(PiPr3)2. Since PhC⋮CD

  末端乙炔RC⋮CH（R = Ph和SiMe 3）与RuH 3 XL 2（X = Cl，I; L = P t Bu 2 Me）的反应在化学计量比为2：1的情况下发生释放RHC CH 2并形成亚乙烯基络合物RuHX（CCHR）L 2。从头算DFT（B3LYP）计算表明，亚乙烯基配合物具有Y结构，Y脚处带有Cl。即使在低温下或与OsH 3 Cl（P我Pr 3）2。由于PhC⋮CD仅形成同位素异构体RuDI（CCHPh）L 2和PhHC CHD，提出了一种机制，其中一个早期事件是在C⋮C键中添加Ru-H。对亚乙烯基配合物形成反应路径的初步计算研究支持了将乙炔插入Ru-H键的这一步骤。