cis,cis,trans-RuCl2(CO)2(P(C(CH3)3)2CH3)2 | 183812-59-1

• 英文名称: cis,cis,trans-RuCl2(CO)2(P(C(CH3)3)2CH3)2
• 英文别名: cis,cis,trans-Ru(CO)2(P(C4H9)2CH3)2Cl2；dicarbonyldichlorobis(methyldi-t-butylphosphine)ruthenium(II)
• CAS: 183812-59-1；40537-26-6
• 化学式: C₂₀H₄₂Cl₂O₂P₂Ru
• 分子量: 548.476
• InChiKey: GMOVVAJSPBIROT-UHFFFAOYSA-L

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

• 作为反应物：
  描述：

  cis,cis,trans-RuCl2(CO)2(P(C(CH3)3)2CH3)2 在 Mg 作用下， 以 四氢呋喃 为溶剂， 以80%的产率得到
  参考文献：
  名称：

  Isolable, Unsaturated Ru(0) in Ru(CO)2(PtBu2Me)2: Not Isostructural with Rh(I) in Rh(CO)2(PR3)2+

  摘要：

  DOI：

  10.1021/ja00139a028
• 作为产物：
  描述：

  carbonylchlorohydridobis(methyldi-t-butylphosphine)ruthenium(II) 在 CH₃Li 作用下， 以 氘代甲苯 、 甲苯 为溶剂， 生成 cis,cis,trans-RuCl2(CO)2(P(C(CH3)3)2CH3)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

• Reactivity of RuCl₂(CO)(P<i>^t</i>Bu₂Me)₂ toward H₂ and Brønsted Acids:  Aggregation Triggered by Protonation and Phosphine Loss
  作者：Dejian Huang、Kirsten Folting、Kenneth G. Caulton

  DOI：10.1021/ic9605837

  日期：1996.1.1

  Reaction of H-2 with RuCl2(CO)L(2) (L = P(t)Bu(2)Me) in benzene forms RuHCl(CO)L(2) and HCl. The latter reacts with RuCl2(CO)L(2) to give [LH][Ru2Cl5(CO)(2)L(2)] and [LH]Cl. The Ru2Cl5(CO)(2)L(2)(-) ion is detected (NMR) as several isomers, and is shown by X-ray diffraction to have a face-shared bioctahedral structure: LCl(OC)Ru(mu-Cl)(3)Ru(CO)ClL(-). The loss of phosphine from Ru(II) is triggered by electrophilic attack, but not directly on P or on the Ru-P bond. It is shown (low-temperature NMR studies) that HCl reacts with RuHCl(CO)L(2) to give initially RuCl2(H-2)(CO)L(2), in which H-2 is trans to Cl. From this study, and also direct observation of the reaction of HCl with RuCl2(CO)L(2) to produce Ru2Cl5(CO)(2)L(2)(-), the Bronsted basicity of chloride in RuCl2(CO)L(2) is established. This accounts for its reaction with PhC(2)H and NEt(3) to give Ru(C(2)Ph)Cl(CO)L(2). Crystallographic data (-173 degrees C) for [P(t)Bu(2)MeH][Ru2Cl5(CO)(2)(P(t)Bu(2)Me)(2)]: a = 16.418(2)Angstrom, b = 12.578(2)Angstrom, c = 20.044(3)Angstrom, beta = 103.38(1)degrees with Z = 4 in space group P2(1)/a.
• 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
• Five-coordinate complexes [RuHCl(CO)(PBut2R)2] (R = Me or Et) formed from ruthenium trichloride and the Tertiary Phosphine in 2-methoxyethanol
  作者：Derek F. Gill、Bernard L. Shaw

  DOI：10.1016/s0020-1693(00)91632-3

  日期：1979.1