Ru(CO)3(P((t)Bu)2Me)2 | 183555-69-3

• 英文名称: Ru(CO)3(P((t)Bu)2Me)2
• CAS: 183555-69-3
• 化学式: C₂₁H₄₂O₃P₂Ru
• 分子量: 505.58
• InChiKey: IFOZPUUVEOHHMT-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
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• 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

• 作为产物：
  描述：

  carbonylchlorohydridobis(methyldi-t-butylphosphine)ruthenium(II) 在 CH₃Li 作用下， 以 氘代苯 、 甲苯 为溶剂， 生成 Ru(CO)3(P((t)Bu)2Me)2
  参考文献：
  名称：

  Characterization and Reactivity of an Unprecedented Unsaturated Zero-Valent Ruthenium Species:  Isolable, Yet Highly Reactive

  摘要：

  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.

  DOI：

  10.1021/ja960967w

文献信息

• Gas/Solid Reactivity of Unsaturated Ruthenium-Containing Molecular Solids
  作者：Montserrat Oliván、Alexei V. Marchenko、Joseph N. Coalter、Kenneth G. Caulton

  DOI：10.1021/ja971608j

  日期：1997.9.1
• Heyn; Macgregor; Nadasdi, Inorganica Chimica Acta, 1997, vol. 259, # 1-2, p. 5 - 26
  作者：Heyn、Macgregor、Nadasdi、Ogasawara、Eisenstein、Caulton

  DOI：——

  日期：——
• Ligand (L) Influence on CO Binding Enthalpies to Ru(CO)₂L₂
  作者：Chunbang Li、Montserrat Oliván、Steven P. Nolan、Kenneth G. Caulton

  DOI：10.1021/om970220u

  日期：1997.9.1

  Reaction enthalpies for the addition of CO to Ru(CO)(2)L-2 (L = (PBu2Me)-Bu-t, (PPr3)-Pr-i, and PCy3) in toluene are -26.2(3), -31.4(2), and -28.9(4) kcal/mol, respectively. These are larger than the enthalpies of reaction with MeNC, PhC=CPh, and PhCC-H. (PBu2Me)-Bu-t consistently gives the least amount of enthalpy released, but only when CO (and MeNC) is the reagent does (PPr3)-Pr-i yield a more exothermic enthalpy of reaction than. PCy3. The generally subtle influences on Delta H by (PPr3)-Pr-i and PCy3 are rationalized in terms of the contradictory steric and electronic effects as isopropyl is replaced by cyclohexyl.