carbonylchlorohydridobis(methyldi-t-butylphosphine)ruthenium(II) | 105015-57-4

• 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: carbonylchlorohydridobis(methyldi-t-butylphosphine)ruthenium(II)
• 英文别名: Carbon monoxide;chloro(hydrido)ruthenium;ditert-butyl(methyl)phosphane
• CAS: 105015-57-4
• 化学式: C₁₉H₄₃ClOP₂Ru
• 分子量: 486.02
• InChiKey: LLHXUUKEZQQXJR-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  7.77
• 重原子数：
  24
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.95
• 拓扑面积：
  1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  carbonylchlorohydridobis(methyldi-t-butylphosphine)ruthenium(II) 在 CH₃Li 作用下， 以 甲苯 、 正戊烷 为溶剂， 生成
  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
• 作为产物：
  描述：

  、 氢气 在 Et₃N 作用下， 以 苯 为溶剂， 生成 carbonylchlorohydridobis(methyldi-t-butylphosphine)ruthenium(II)
  参考文献：
  名称：

  Reactivity of RuCl₂(CO)(P^tBu₂Me)₂ toward H₂ and Brønsted Acids:  Aggregation Triggered by Protonation and Phosphine Loss

  摘要：

  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.

  DOI：

  10.1021/ic9605837

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。
• 14-Electron Four-Coordinate Ru(II) Carbyl Complexes and Their Five-Coordinate Precursors:  Synthesis, Double Agostic Interactions, and Reactivity
  作者：Dejian Huang、William E. Streib、John C. Bollinger、Kenneth G. Caulton、Rainer F. Winter、Thomas Scheiring

  DOI：10.1021/ja990621w

  日期：1999.9.1

  five-coordinate Ru(II) complexes RuHCl(CO)(PiPr3)2, 1, RuCl2(CO)(PiPr3)2, 2, and Ru(Ph)Cl(CO)(PtBu2Me)2, 12, are reported. All three of these complexes have square-based pyramid geometry with the strongest σ-donor ligand trans to the vacant site. These 16-electron complexes do not show bona fide agostic interactions. This is attributed to the strong trans influence ligand (H, CO, and Ph) and π-donation

  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
• Hindered rotation about single bonds in RuHX(CO)(PtBu2Me)2 and IrHCl2(PtBu2Me)2
  作者：J. Ulrich Notheis、Richard H. Heyn、Kenneth G. Caulton

  DOI：10.1016/0020-1693(94)04244-p

  日期：1995.2

  The molecules RuCl(Ph)(CO)L 2 and RuH(Ph)(CO) 2 L 2 exhibit slow ( 1 H and 13 C NMR time scales) rotation about the RuC( ipso ) bond at 23 °C. Already at 23 °C, IrL 2 Cl 2 H shows 1 H and 31 P NMR evidence for two equally abundant (mirror symmetric) conformers due to hindered rotation about IrP bonds.

  摘要Ru [C（O）Me] I（CO）L 2（L = P t Bu 2 Me）显示了两个构象的存在的1 H和31 P NMR证据（通过其关于RuP键的旋转构象加以区分）它们显示（在− 80°C下）（a）没有对称性，（b）镜面对称性（由Ru [C（O）Me] I（CO）平面定义）。RuH（Cl）（CO）L 2也是同样。Ru（Me）I（CO）L 2显示（1 H和31 P证据）两个构象异构体，每个镜像对称，具有比乙酰基类似物更低的互转换垒。分子RuCl（Ph）（CO）L 2和RuH（Ph）（CO）2 L 2在23°C下围绕RuC（ipso）键表现出缓慢的（1 H和13 C NMR时间标度）旋转。IrL 2 Cl 2 H早在23°C时，由于绕Ir HP键旋转受阻，显示出两个同等丰富（镜对称）构象异构体的1 H和31 P NMR证据。
• RuX(CO)(NO)L₂ and Ru(CO)(NO)L₂⁺:  Ru(0) or Ru(II) or In Between?
  作者：Masamichi Ogasawara、Dejian Huang、William E. Streib、John C. Huffman、Nuria Gallego-Planas、Feliu Maseras、Odile Eisenstein、Kenneth G. Caulton

  DOI：10.1021/ja970563j

  日期：1997.9.1

  [Ru(NO)(CO)L2](BArF4) show a ΔG⧧ (100 °C) for inversion through planar Ru of 19.1 kcal/mol. Ru(η1-BF4)(CO)(NO)L2 is shown by X-ray diffraction to have a square-pyramidal structure with apical bent NO. The IR frequencies of NO and CO are analyzed to conclude that all five-coordinate species except Ru(NO)(CO)2L2+ and RuH(NO)(CO)L2 have bent nitrosyls; these last two have linear NO. RuX(CO)(NO)(PH3)2+ (X = Cl-

  报道了 RuCl(CO)(NO)L2 (L = PtBu2Me) 的合成和 Cl- 被 BF4-、CO、CH3CN、H2O、F- 和 H- 的替代。NaBArF4 (ArF = 3,5-(CF3)2C6H3) 去除卤化物以产生四配位的 16 电子阳离子 Ru(NO)(CO)L2+，X 射线衍射显示具有非平面结构，表明更多的背键比等电子 Ru(CO)2L2。[Ru(NO)(CO)L2](BArF4) 中 tBu 基团的变温 1H NMR 研究表明，通过平面 Ru 进行反转的 ΔG⧧ (100 °C) 为 19.1 kcal/mol。通过 X 射线衍射显示 Ru(η1- )(CO)(NO)L2 具有带有顶端弯曲 NO 的方形锥体结构。分析 NO 和 CO 的 IR 频率得出结论，除 Ru(NO)(CO)2L2+ 和 RuH(NO)(CO)L2 之外的所有五配位物质都具有弯曲的亚硝基；这最后
• Poulton, Jason T.; Hauger, Bryan E.; Kuhlman, Roger L., Inorganic Chemistry, 1994, vol. 33, # 15, p. 3325 - 3330
  作者：Poulton, Jason T.、Hauger, Bryan E.、Kuhlman, Roger L.、Caulton, Kenneth G.

  DOI：——

  日期：——