[RuCl2(PiPr3)2(CO)2] | 183812-60-4

• 英文名称: [RuCl2(PiPr3)2(CO)2]
• CAS: 183812-60-4；160730-94-9
• 化学式: C₂₀H₄₂Cl₂O₂P₂Ru
• 分子量: 548.476
• InChiKey: WCAJBTZXHNHSMV-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：

  [RuCl2(PiPr3)2(CO)2] 在 Mg 作用下， 以 四氢呋喃 为溶剂， 以83%的产率得到Ru(CO)2(P(i)Pr₃)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
• 作为产物：
  描述：

  [RuCl(η1-OCMe2)(CO)2(PPr(i)3)2]BF4 在 NaCl 作用下， 以 not given 为溶剂， 生成 [RuCl2(PiPr3)2(CO)2]
  参考文献：
  名称：

  合成，反应性和催化活性[期RuH（η 1 -OCMe 2）（CO）2（PPR我3）2 ] BF 4

  摘要：

  所述solvento络合物[期RuH（η 1 -OCMe 2）（CO）2（PPR我3）2 ] BF 4 2，它是苯乙炔的苯乙烯的独家氢化和相同的炔氢化硅烷化的活性催化剂的顺式- PhCH CH（SiEt 3），是通过[Ru（H）Cl（OC）2（Pr i 3 P）2 ] 1与AgBF 4在丙酮中的溶剂反应制得的。已经研究了2的反应性。该化合物与路易斯碱（L）反应生成[RuH（CO）2 L（PPri 3） 2 ] BF 4 [L ＝ H 2 O 3，MeCN 4，CO 5或吡唑（Hpz） 6 ]。配合物5可以用KOH进行质子化反应，得到[Ru（OC） 3（Pr i 3 P） 2 ] 7，而6与[{Rh（µ-OMe）（di烯烃）} 2 ] [二烯烃=四氟苯并戊烯（ tfbb）或环辛-1,5-二烯（cod）]生成式[（OC） 2（Pr i 3 P） 2 Ru（µ-H）（µ-pz）Rh（di烯烃）]

  DOI：

  10.1039/dt9950002171

文献信息

• Werner, Helmut; Tena, Miguel Angel; Mahr, Norbert, Chemische Berichte, 1995, vol. 128, # 1, p. 41 - 48
  作者：Werner, Helmut、Tena, Miguel Angel、Mahr, Norbert、Peters, Karl、Schnering, Hans-Georg von

  DOI：——

  日期：——
• Coupling of terminal alkynes by RuHXL2 (X=Cl or N(SiMe3)2, L=PiPr3)
  作者：Joo-Ho Lee、Kenneth G. Caulton

  DOI：10.1016/j.jorganchem.2007.12.016

  日期：2008.4

  The compounds RuL(2)HX, where L = P(i)Pr(3) and X = Cl or N(SiMe(3))(2), are catalyst precursors for dimerization of terminal alkynes to enynes and also to cumulenes at 23 degrees C; selectivity among these products is X-dependent, but not high. Conversion of Ru species onto the catalytic cycle was undetectably small, so alternative approaches to understanding the catalytic mechanism were employed: stoichiometric reactions, independent synthesis of candidate intermediates, and trapping with CO. These show the intermediacy of vinylidenes and vinyl compounds, and reveal conversion of cumulenes to the thermodynamically more stable enynes. (C) 2007 Elsevier B.V. All rights reserved.