(η5-C5Me5)(PMe3)2Ru(CH2SiMe3) | 87640-52-6

• 英文名称: (η5-C5Me5)(PMe3)2Ru(CH2SiMe3)
• CAS: 87640-52-6
• 化学式: C₂₀H₄₄P₂RuSi
• 分子量: 475.672
• InChiKey: BVLMOIRIVVXSQC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 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：

  (η5-C5Me5)(PMe3)2Ru(CH2SiMe3) 、 三氯硅烷 在 PMe₃ 作用下， 以 甲苯 为溶剂， 以22%的产率得到(η5-C5Me5)(PMe3)2ruthenium(SiCl3)
  参考文献：
  名称：

  合成与性能研究类型的钌配合物的硅烯[（η的5 -C 5我5）（ME 3 P）2 RuSiX 2 ] +（X =硫醇盐，Me和pH下）

  摘要：

  类型的Cp *的各种钌配合物的甲硅烷基（ME 3 P）2 RuSiR 3（CP * =η 5 -C 5我5 ; SIR 3 =的SiCl 3（1），硅（NME 2）3（2），硅（ SEt）3（3），Si（S-2-Naph）3（4），（5），Si（SCy）2 Cl（6）和Si（SMes）2 Cl（7，Mes = 2,4，通过Cp *（Me 3 P）反应制备6-三甲基苯基））2 RuCH 2 SiMe 3和合适的硅烷HSiR 3。通过3与Me 3 SiOTf的反应，将化合物3转化为三氟甲磺酸酯Cp *（Me 3 P）2 RuSi（SEt）2 OTf（8）。类似的反应产生了Cp *（Me 3 P）2 RuSi（NMe 2）2 OTf（13），Cp *（Me 3 P）2 RuSi（NMe 2）（OTf）2（14），Cp *（Me 3 P）2个RuSi（SMes）2 OTf（18）和Cp *（Me 3

  DOI：

  10.1021/om980506e
• 作为产物：
  描述：

  [(pentamethylcyclopentadienyl)RuCl(PMe3)2] 、 (三甲基硅基)甲基氯化镁 以 乙醚 、 甲苯 为溶剂， 以73%的产率得到(η5-C5Me5)(PMe3)2Ru(CH2SiMe3)
  参考文献：
  名称：

  Don Tilley; Grubbs, Robert H.; Bercaw, John E., Organometallics, 1984, vol. 3, # 2, p. 274 - 278

  摘要：

  DOI：

文献信息

• Stoichiometric and Catalytic Behavior of Cationic Silyl and Silylene Complexes
  作者：Steven R. Klei、T. Don Tilley、Robert G. Bergman

  DOI：10.1021/om0203173

  日期：2002.10.1

  Reactions of Ir(III) silyl and silylene complexes with a variety of unsaturated substrates were investigated. The reactivity of these complexes toward small molecules was also examined, and this led to the discovery of a nitrile carbon−carbon bond cleavage under mild conditions. Both silyl and silylene complexes of Ir(III) are precatalysts for catalytic hydrosilylation of ketones, and the mechanism

  研究了Ir（III）甲硅烷基和亚甲硅烷基络合物与各种不饱和底物的反应。还检查了这些复合物对小分子的反应性，这导致在温和条件下发现腈碳-碳键断裂的发现。Ir（III）的甲硅烷基和亚甲硅烷基络合物都是酮催化氢化硅烷化的预催化剂，并讨论了该反应的机理。在研究催化反应机制的过程中，形式类似的新的钌配合物的亚甲硅烷的[CP *（PME 3）2的Ru（SIR 2）] [B（C 6 ˚F 5）4 ]（CP * =η 5 -C 5我5，R =我PR，SPH）被准备。还进行了[CP *（PMe 3）Ir（SiPh 2）（H）] [B（C 6 F 5）4 ]与已知的路易斯酸氢化硅烷化催化剂B（C 6 F 5）3的比较。
• Preparation, characterization, and x-ray crystal structure of an acetonitrile-complexed ruthenium silylene
  作者：Daniel A. Straus、T. Don Tilley、Arnold L. Rheingold、Steven J. Geib

  DOI：10.1021/ja00253a062

  日期：1987.9

  (L/sub n/M double bond SiR/sub 2/) are postulated intermediates in a number of transition-metal-mediated transformations, including Rochow's direct process, catalytic redistribution of silanes, and various silylene-transfer reactions. Unfortunately, such species have been synthetically elusive, despite the well-established existence of congeneric carbene, germylene, stannylene, and plumbylene complexes

  亚甲硅烷配合物 (L/sub n/M 双键 SiR/sub 2/) 是许多过渡金属介导的转化中假定的中间体，包括 Rochow 的直接过程、硅烷的催化再分配和各种亚甲硅烷转移反应。不幸的是，尽管同类卡宾、亚锗烯、亚锡和铅烯配合物的存在已经确立，但这些物种在合成上是难以捉摸的。尽管存在许多亚甲硅烷桥连双金属物种的例子，但没有充分表征的具有形式金属-硅双键的化合物的例子，尽管有很多尝试来制备它们。为了研究过渡金属 - 硅双键的化学性质，作者正在尝试开发此类末端亚甲硅烷配合物的合成路线。
• Synthesis, structure and dynamic studies on base-stabilized silylene complexes
  作者：Steven K. Grumbine、Daniel A. Straus、T. Don Tilley、Arnold L. Rheingold

  DOI：10.1016/0277-5387(94)00367-n

  日期：1995.1

  The silyl complexes Cp*(PMe(3))(2)RuSiX(2)Z (Cp* = eta(5)-C(5)Me(5); 1, SiX(2)Z = Si[S(Tol-p)](3); 2, SIX(2)Z = Si[O(Tol-p)](3); 3, SiX(2)Z = SiMe(2)[S(Tol-p)]), prepared by reaction of the appropriate hydrosilane with Cp* (PMe(3))(2)RuCH(2)SiMe(3), react with Me(3)SiOTf (OTf = OSO2CF3) to afford the triflato(silyl) complexes Cp*(PMe(3))(2)RuSiX(2)OTf (4, X = S(Tol-p); 5, X = O(Tol-p); 6, X = Me) or Cp*(PMe(3))(2)Rusi[S(Tol-p)](OTf)(2) (7). The X-ray crystal structures of the compounds 1, 4, and 7 are described and discussed. Compound 4 reacts with LiBEt(3)H to produce Cp*(PMe(3))(2)RuSiH[S(Tol-p)](2) (8), with water to give Cp*(PMe(3))(2)RuSi[S(Tol-p)](OTf)(OH) (10), and with HCl to afford Cp*(PMe(3))(2) RuSiCl2(OTf) (11). The triflate Cp*(PMe(3))(2)RuSiH[S(Tol-p)](OTf) (9) results from reaction of 8 with Me(3)SiOTf. The base-stabilized silylene complexes [Cp*(PMe(3))2Ru SiX(2)(NCMe)]BPh(4) (13, X = S(Tol-p); 14, X = O(Tol-p); 15, X = Me) are prepared by displacement of triflate from 4-6. The X-ray structures of 13 and 15 are described and compared to the previously reported structure of [Cp*(PMe(3))(2)RuSiPh(2)(NCMe)]BPh(4) (12). The structures are discussed in terms of the amount of incipient silylene character possessed by each. For 12-15, bound acetonitrile exchanges with free acetonitrile in dichloromethane solution via a dissociative mechanism. The rates and activation parameters for these exchange reactions allow an ordering of stabilities for the corresponding base-free silylene complexes, since the reactions involve rate-limiting loss of acetonitrile from the complex. The kinetic data indicate that the stabilizing influences for silylene substituents in this system are ordered according to : S(Tol-p) > O(Tol-p) > Me > Ph. A different ordering is suggested by the X-ray structural data. Apparently conflicting information from the structural and dynamic studies are discussed and rationalized, and it is concluded that the ordering suggested by the kinetic data is more useful.
• Straus, Daniel A.; Zhang, Cheng; Quimbita, Grace E., Journal of the American Chemical Society, 1990, vol. 112, # 7, p. 2673 - 2681
  作者：Straus, Daniel A.、Zhang, Cheng、Quimbita, Grace E.、Grumbine, Steven D.、Heyn, Richard H.、Tilley, T. Don、Rheingold, Arnold L.、Geib, Steven J.

  DOI：——

  日期：——
• Lin, Wenbin; Wilson, Scott R.; Girolami, Gregory S., Organometallics, 1994, vol. 13, # 6, p. 2309 - 2319
  作者：Lin, Wenbin、Wilson, Scott R.、Girolami, Gregory S.

  DOI：——

  日期：——