[RuH2(CO)2(P(t-Bu)2Me)2] | 167774-62-1

• 英文名称: [RuH2(CO)2(P(t-Bu)2Me)2]
• 英文别名: cis,cis,trans-Ru(H)2(CO)2(P((t)Bu)2Me)2
• CAS: 167774-62-1
• 化学式: C₂₀H₄₄O₂P₂Ru
• 分子量: 479.586
• InChiKey: XEYFZHVJYBXDKH-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：

  [RuH2(CO)2(P(t-Bu)2Me)2] 以 neat (no solvent) 为溶剂， 生成
  参考文献：
  名称：

  Heyn; Macgregor; Nadasdi, Inorganica Chimica Acta, 1997, vol. 259, # 1-2, p. 5 - 26

  摘要：

  DOI：
• 作为产物：
  描述：

  在 氢气 作用下， 生成 [RuH2(CO)2(P(t-Bu)2Me)2]
  参考文献：
  名称：

  Gas/Solid Reactivity of Unsaturated Ruthenium-Containing Molecular Solids

  摘要：

  DOI：

  10.1021/ja971608j

文献信息

• Facile and Reversible Cleavage of C−F Bonds. Contrasting Thermodynamic Selectivity for RuCF₂H vs FOsCFH
  作者：Dejian Huang、Patrick R. Koren、Kirsten Folting、Ernest R. Davidson、Kenneth G. Caulton

  DOI：10.1021/ja001646u

  日期：2000.9.1

  substituents are inequivalent. Having hydride trans to the CF2 ligand, MHF(CF2)(CO)L2 is a kinetic product, which converts to a thermodynamic isomer. For Ru, the final product is a 16e complex, RuF(CF2H)(CO)L2, formed by combination of CF2 and hydride. For Os, the product is an 18e complex, OsF2(CFH)(CO)L2, resulting from exchange of one carbene fluoride with the hydride. The distinct difference between

  在催化量的 F-(CsF) 存在下，Me3SiRf（Rf = CF3 和 C6F5）与 16 电子络合物 MHF(CO)L2（M = Ru、Os；L = PiPr3、PtBu2Me）的氟化物交换 Rf通过 α-氟迁移得到 Me3Si-F 和不饱和五氟苯基配合物 MH( )(CO)L2 或（当 Rf = ）饱和氟卡宾配合物 MHF(CF2)(CO)L2。X 射线晶体结构和溶液 19F NMR 研究表明，在基态下，CF2 基团的三个原子位于垂直于 P-Ru-P 轴的平面内，从而使 π-back-donation 最大化，并且卡宾取代基是不等价的。MHF(CF2)(CO)L2 与 CF2 配体发生氢化物反式，是一种动力学产物，可转化为热力学异构体。对于 Ru，最终产物是 16e 络合物 RuF(CF2H)(CO)L2，由 CF2 和氢化物结合形成。对于奥斯，产物是一种 18e 络合物
• Characterization and Reactivity of an Unprecedented Unsaturated Zero-Valent Ruthenium Species:  Isolable, Yet Highly Reactive
  作者：Masamichi Ogasawara、Stuart A. Macgregor、William E. Streib、Kirsten Folting、Odile Eisenstein、Kenneth G. Caulton

  DOI：10.1021/ja960967w

  日期：1996.1.1

  Magnesium reduction of cis,cis,trans-RuCl2(CO)(2)L(2) (L = P(t)Bu(2)Me) yields isolable Ru(CO)(2)L(2), shown by solution spectroscopies and X-ray diffraction to have trans phosphines but cis carbonyls, in a nonplanar structure which resembles a trigonal bipyramid with one equatorial ligand missing. This unusual geometric structure is traced by ab initio (MP2) study to enhanced back-donation to CO by zero-valent Ru. This molecule reacts in time of mixing to add CO, MeNC, O-2, CS2, C2H4, or PhC=CPh. Rapid oxidative addition occurs with H-2, HCl, Cl-2, and PhC=CH. Oxidative addition is slower with MeCl, Me(3)SiH, and MeOH, which leads to more complicated reaction schemes. Reaction with PPh(2)H gives not oxidative addition but addition and displacement, yielding Ru(CO)(2)-(PPh(2)H)(2)(P(t)Bu(2)Me) and equimolar free P(t)Bu(2)Me. Magnesium reduction of cis,cis,trans-RuCl2(CO)(2)L'(2) proceeds analogously for L' = (PPr3)-Pr-t, but for L' = PPh(3), decomposition and ligand scavenging give Ru(CO)(2)(PPh(3))(3). Reduction of cis,trans-RuCl2(CO)(CNMe)L(2) gives the product of oxidative addition of a (t)Bu C-H bond: RuH(CO)(CNMe)-[eta(2)-P(CMe(2)CH(2))(t)BuMe]L, showing the influence of electron density at unsaturated Ru(O) on its persistence.