Ru(Me)Cl(CO)(P(t)Bu2Me)2 | 183555-80-8

• 英文名称: Ru(Me)Cl(CO)(P(t)Bu2Me)2
• CAS: 183555-80-8；219538-90-6
• 化学式: C₂₀H₄₅ClOP₂Ru
• 分子量: 500.047
• InChiKey: GPWKTOBVNVQRBI-UHFFFAOYSA-M

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：

  Ru(Me)Cl(CO)(P(t)Bu2Me)2 、 cesium fluoride 以 丙酮 为溶剂， 以54%的产率得到Ru(Me)F(CO)(P(t)Bu2Me)2
  参考文献：
  名称：

  14 电子四配位 Ru(II) Carbyl 配合物及其五配位前体：合成、双极性相互作用和反应性

  摘要：

  五配位 Ru(II) 配合物 RuHCl(CO)(PiPr3)2, 1, RuCl2(CO)(PiPr3)2, 2 和 Ru(Ph)Cl(CO)(PtBu2Me)2, 12 的结构是报道。所有这三种复合物都具有基于正方形的金字塔几何形状，其中最强的 σ-供体配体转移到空位。这些 16 电子复合物没有表现出真正的激动相互作用。这归因于强反式影响配体（H、CO 和 Ph）和 Cl 的 π 供体，这进一步得到以下事实的支持：12 的 Cl-去除产物中存在两种激动相互作用，即四配位 [RuPh(CO)L2]BAr'4 (L = PtBu2Me, Ar' = 3,5-C6H3(CF3)2), 16. 16 和 12 的结构比较表明去除 Cl- 不会改变剩余的配体排列，但为激动相互作用创造了两个低洼的 LUMO，IR 光谱证明它们在溶液中持续存在。16 与 E-H (E = B, C(sp)) 键的反应裂解

  DOI：

  10.1021/ja990621w
• 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(Me)Cl(CO)(P(t)Bu2Me)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

• Mechanistic and thermodynamic aspects of methylene transfer from CH2N2 to MHCl(CO)L2 (M=Ru, Os; L=tertiary phosphine): non-least motion behavior and extreme dependence on phosphine identity
  作者：Dejian Huang、Greg J. Spivak、Kenneth G. Caulton

  DOI：10.1039/a803432j

  日期：——

  Reaction of MHCl(CO)(PBut2Me)2 (M=Ru and Os) with CH2N2 was studied from -78 to 25°C, revealing first the formation of MHCl(CH2)(CO)(PBut2Me)2, where the carbene ligand CH2 occupies what was the open coordination site of MHCl(CO)(PBut2Me)2, which lies trans to the hydride. This intermediate then isomerizes to M(CH3)Cl(CO)(PBut2Me)2, below 25°C for each metal. The analogous reaction of MHCl(CO)(PPri3)2 with CH2N2 does indeed give MHCl(CH2)(CO)(PPri3)2, which then ‘decomposes’ unselectively; when M=Os, C2H4 and OsHCl(CO)(PPri3)2 are among the products. This extreme phosphine dependence is attributed to the H–MCH2 to M(CH3) isomerization requiring phosphine dissociation; the smaller PPri3 fails to dissociate at a rate competitive with alternative decomposition reactions.

  MHCl(CO)(PBut2Me)2（M=Ru和Os）与CH2N2的反应在-78°C到25°C的范围内进行了研究，首先形成了MHCl(CH2)(CO)(PBut2Me)2，其中类卡宾配体 占据了MHCl(CO)(PBut2Me)2的开放配位位点，且该位点位于氢化物的对面。该中间体随后异构化为M(CH3)Cl(CO)(PBut2Me)2，且对于每种金属，该异构化反应在25°C以下发生。MHCl(CO)(PPri3)2与 的类似反应确实生成了MHCl( )(CO)(PPri3)2，但随后会无选择性地“分解”；当M=Os时，C2H4和OsHCl(CO)(PPri3)2是其中的一些产物。这种极端的膦依赖性被归因于H–MCH2到M( )的异构化需要膦的解离；较小的PPri3未能以与其他分解反应竞争的速度解离。