[bis(dimethylphosphanylmethyl)-methylsilyl]methyl-dimethylphosphane;dichlororuthenium;trimethylphosphane | 136371-95-4

• 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: [bis(dimethylphosphanylmethyl)-methylsilyl]methyl-dimethylphosphane;dichlororuthenium;trimethylphosphane
• CAS: 136371-95-4
• 化学式: C₁₃H₃₆Cl₂P₄RuSi
• 分子量: 516.385
• InChiKey: YVMCQAQWVGBQDM-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  6.64
• 重原子数：
  21.0
• 可旋转键数：
  1.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为反应物：
  描述：

  [bis(dimethylphosphanylmethyl)-methylsilyl]methyl-dimethylphosphane;dichlororuthenium;trimethylphosphane 在 双(三甲基硅烷基)氨基钾 作用下， 以 四氢呋喃 为溶剂， 以84%的产率得到[bis(dimethylphosphanylmethyl)-methylsilyl]methyl-dimethylphosphane;chlororuthenium(1+);trimethylphosphane
  参考文献：
  名称：

  Regiocontrol of Cyclometalation in a P₄Ru(II) System. Unusual Base-Induced Metalation within a Chelate Ring versus Activation of a Methyl Group

  摘要：

  The internally cyclometalated complex (MeSi-(CH2PMe2)(2)CHPMe2)(PMe3)RuH has been prepared by the treatment of MeSi(CH2PMe2)(3)PMe3Ru(H)(Cl) with base, and an analogue has been structurally characterized by X-ray diffraction. The externally cyclometalated isomer MeSi(CH2PMe2)(3)PMe2CH2RuH has been cleanly generated by the thermolysis of MeSi(CH2PMe2)(3)PMe3-Ru(H)(Me), and the two isomers have been contrasted in terms of their spectroscopic features, calculated energies, and relative reactivities toward cresol and H-2. The two isomers are surprisingly resistant to interconversion. A chloride derivative, (MeSi(CH2PMe2)(2)CHPMe2)(PMe3)-RuCl, has also been prepared, and its reactivity has shown the internally cyclometalated framework to be surprisingly stable.

  DOI：

  10.1021/om0202470
• 作为产物：
  描述：

  dichlorotetrakis(trimethyl phosphite)ruthenium(II) 以 甲苯 为溶剂， 以88%的产率得到[bis(dimethylphosphanylmethyl)-methylsilyl]methyl-dimethylphosphane;dichlororuthenium;trimethylphosphane
  参考文献：
  名称：

  Oligophosphan-Liganden：XXXIII。分子内部的Spaltungen von sp 2-和sp 3 -CH-Bindungenan L 4 Ru 0 -Komplexrümpfenmit P（0 -C 6 H 4 PMe 2）3，N（CH 2 CH 2 PMe 2）3， MeP（CH 2 CH 2 CH 2 PMe 2）2 / PR 3和MeSi（CH 2 PMe 2）3 / PR 3 （R = Me，OMe）阿尔斯·斯蒂格利根登（Stützliganden）

  摘要：

  同时尝试通过用Na（Hg ）还原（pp 3）RuCl 2（1）来制备组成为（pp 3）RuH（Ar）（pp 3 = P（0 -C 6 H 4 PMe 2）3）的配合物）在苯，甲苯和二甲苯中的分离仍不成功，在室温下顺利进行了C 6 H 6中pp同系物（pp 3）OsCl 2（2）的钠汞齐还原，得到了（pp 3 OsH（C 6 H 5）（ 7）。氢化苯基衍生物（pp2）[（MeO）3 P] RuH（C 6 H 5）（13）和（sip 3）（Me 3 P）RuH（C 6 H 5）（14）（pp 2 = MeP（CH 2 CH 2 CH 2 PME 2）2，抿3 = MESI（CH 2 PME 2）3（PP）均类似地通过还原用Na（汞柱的苯溶液获得）2）[（MEO）3 P]的RuCl 2（5）和（抿3）（Me 3 P）RuCl 2（6）。在回流的苯中用钠汞齐处理（np 3）RuCl 2（3）（np

  DOI：

  10.1016/0022-328x(91)83050-e

文献信息

• C−C and C−H Bond Activation at Ruthenium(II):  The Stepwise Degradation of a Neopentyl Ligand to a Trimethylenemethane Ligand
  作者：Kristopher McNeill、Richard A. Andersen、Robert G. Bergman

  DOI：10.1021/ja972131e

  日期：1997.11.1

  Ruthenacyclobutane complexes (SiP3)(PMe3)Ru(CH2EMe2CH2) (SiP3 = MeSi(CH2PMe2)3; 1, E = C; 2, E = Si) were synthesized from (SiP3)(PMe3)RuCl2 (3) and 2 equiv of the Grignard reagents, Me3ECH2MgCl. Metallacycle 1 was found to reversibly interconvert with the allyl complex (SiP3)Ru(Me)(η3-CH2CMeCH2) (4) and PMe3 when heated above 75 °C. From the results of kinetic studies and thermolysis of labeled material

  钌环丁烷配合物 (SiP3)(PMe3)Ru(CH2EMe2 ) (SiP3 = MeSi( PMe2)3; 1, E = C; 2, E = Si) 由 (SiP3)(PMe3)RuCl2 (3) 和 2 当量的格氏试剂，Me3ECH2MgCl。当加热到 75 °C 以上时，发现金属环 1 与烯丙基络合物 (SiP3)Ru(Me)(η3- CMECH ) (4) 和 PMe3 可逆地相互转化。根据标记材料的动力学研究和热解的结果，建议通过可逆的 β-甲基消除/插入进行相互转化。1 到 4 的转化是一个吸热过程（ΔH° = 14.3 ± 1.1 kcal mol-1），但由于 PMe3 配体的丢失，它是熵有利的（ΔS° = 40.9 ± 2.8 cal K-1 mol-1） . β-插入的激活参数确定为 ΔH⧧ = 26.0 ± 1.2 kcal mol-1 和 ΔS⧧ = -10
• Oligophosphan-Liganden
  作者：L. Dahlenburg、K.-M. Frosin、S. Kerstan、D. Werner

  DOI：10.1016/0022-328x(91)83145-t

  日期：1991.4

  The complexes L4RuH(C6H5) with L4 = P(CH2CH2CH2PMe2)3, N(CH2CH2PPh2)3, and MeSi(CH2PMe2)3/PMe3 all serve as catalysts for the dimerization of 1-alkynes, RC-CH (R = C6H5, n-C4H9, t-C4H9). The reaction proceeds to yield 1,4-disubstituted 1-en-3-ynes, RCH = CHC-CR, with varying E/Z stereoselectivities, presumably via intermediates containing 1-en-3-yn-2-yl ligands, -C(C-CR) = CHR. The X-ray structure analysis of (pp3)RuH(C6H4CF3-3) (pp3 = P(CH2CH2CH2PMe2)3) which is available from (pp3)RuCl2 by reduction with sodium amalgam in C6H5CF3 but not from (pp3)RuH(C6H5) and C6H5CF3 by transmetalation, is also reported.
• Becker, Corinna; Dahlenburg, Lutz; Kerstan, Sabine, Zeitschrift fur Naturforschung, B: Chemical Sciences, 1993, vol. 48, # 5, p. 577 - 582
  作者：Becker, Corinna、Dahlenburg, Lutz、Kerstan, Sabine

  DOI：——

  日期：——
• Interconversion of a 3,3-Dimethylruthenacyclobutane and a Methyl(2-methallyl)ruthenium Complex: The First Direct Observation of Reversible .beta.-Methyl Elimination/Migratory Insertion
  作者：Kristopher McNeill、Richard A. Andersen、Robert G. Bergman

  DOI：10.1021/ja00117a037

  日期：1995.3