RuH(PMe3)3(η2-C2H4) | 96570-88-6

• 英文名称: RuH(PMe3)3(η2-C2H4)
• 英文别名: (PMe3)4Ru(C2H4)
• CAS: 96570-88-6
• 化学式: C₁₄H₄₀P₄Ru
• 分子量: 433.437
• InChiKey: QLYUDOSIERUBSF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  RuH(PMe3)3(η2-C2H4) 在 H₂O 作用下， 以 not given 为溶剂， 以30%的产率得到cis-[Ru(PMe3)4(H)(OH)]
  参考文献：
  名称：

  Burn, Melinda J.; Fickes, Michael G.; Hartwig, John F., Journal of the American Chemical Society, 1993, vol. 115, # 13, p. 5875 - 5876

  摘要：

  DOI：
• 作为产物：
  描述：

  cis-Ru(PMe3)4MeCl 、 diethyl magnesium 以 乙醚 为溶剂， 生成 RuH(PMe3)3(η2-C2H4)
  参考文献：
  名称：

  钌与三甲基膦和双（1,2-二甲基膦基）乙烷的烷基，氢化物和相关化合物。顺式-氢化乙基四（三甲基膦）-钌（II）和乙烯四-（三甲基膦）钌（0）的X射线晶体结构

  摘要：

  摘要根据反应条件和烷基的不同，反式RuCl2（PMe3）4与R2Mg的相互作用给出R =（C2H4）Ru（PMe3）4或顺式Ru（H）（C2H5）（PMe3）4。乙基和顺式Ru（H）（nC3H7（PMe3）4对于R =正丙基。Et2Mg与反式RuX2（dmpe）2（X = Cl，CO2Me）的相互作用产生顺式（Rut（Et2）dmpe对于X = Cl为2）或对于X = CO2Me为反式Ru（Et）2（dmpe）2）。（C2H4）Ru（PMe3）4的NMR数据表明，乙烯以η2或金属环丙烷的形式结合，这已通过单晶X射线衍射研究得到证实。这表明“乙烯”碳之间的碳-碳键间距离相对较长，为1.44（1）A。单晶X射线衍射研究也证实了顺式Ru（H）（C2H5）（PMe3）4的结构。考虑观察到的反应性的可能机制。

  DOI：

  10.1016/s0277-5387(00)84672-0

文献信息

• Mechanism of the carbon-carbon cleavage of acetone by the ruthenium benzyne complex (PMe3)4Ru(.eta.2-C6H4): formation and reactivity of an oxametallacyclobutane complex
  作者：John F. Hartwig、Robert G. Bergman、Richard A. Andersen

  DOI：10.1021/ja00164a067

  日期：1990.4

  Generation et caracterisation d'un intermediaire potentiel de la reaction, le complexe (methyl-4 phenyl-4)oxa-1 ruthena-2 cyclobutane

  Generation et caracterisation d'un intermediaire potentiel de la reaction, le complexe (methyl-4 phenyl-4)oxa-1 ruthena-2 cyclobutane
• Solution Calorimetric Investigation of Oxidative Addition of HEAr (E = O, S, Se; Ar = C₆H₄X, X = CH₃, H, Cl, NO₂) to (PMe₃)₄Ru(C₂H₄):  Relationship between HEAr Acidity and Enthalpy of Reaction
  作者：Jinkun Huang、Chunbang Li、Steven P. Nolan、Jeffrey L. Petersen

  DOI：10.1021/om980253p

  日期：1998.8.1

  The enthalpies of reactions of (PMe3)(4)Ru(C2H4) (1) with a series of HEAr compounds (E = O, S, Se; Ar = aryl), leading to the formation of (PMe3)(4)Ru(H)(EAr) complexes, have been measured by anaerobic solution calorimetry in C6H6 at 30.0 degrees C. These reactions are rapid and quantitative under the calorimetry conditions. The measured reaction enthalpies span a range of some 35 kcal/mol. The relative stability scale established is as follows: (PMe3)(4)Ru(H)(OC6H4-p-CH3) < (PMe3)(4)Ru(H)(OC6H5) < (PMe3)(4)Ru(H)(OC6H4-p-Cl) < (PMe3)(4)Ru(H)(OC6H4-p-NO2) < (PMe3)(4)Ru(H)(SC6H4-p-CH3) < (PMe3)(4)Ru(H)(SC6H5) < (PMe3)(4)Ru(H)(SC6H4-p-Cl) approximate to (PMe3)(4)Ru(H)(SeC6H5) < (PMe3)(4)Ru(H)(SC6H4-p-NO2). A single-crystal X-ray structure of one of these complexes, (PMe3)(4)Ru(SC6H5)H (7), is reported. The measured enthalpies of reaction display a dependence on the acidity of HEAr.
• Structure and reactions of oxametallacyclobutanes and oxametallacyclobutenes of ruthenium
  作者：John F. Hartwig、Robert G. Bergman、Richard A. Andersen

  DOI：10.1021/om00055a061

  日期：1991.9

  Structure and reactivity studies are reported with the ruthenium metallacycles prepared as described in the previous paper. A C-C cleavage reaction by an apparent beta-Me elimination pathway at 45-degrees-C is reported for the PMe3-substituted oxametallacyclobutane complex (PMe3)4Ru(OC(Me)(Ph)CH2) (1), while the analogous DMPE-substituted metallacyclobutane (DMPE)2Ru(OC(Me)(Ph)CH2) (2) is stable at 140-degrees-C. Similarly, compound 1 undergoes insertion of CO into the metal-carbon bond, while 2 is inert toward this substrate. Addition of protic acids and electrophiles leads to rapid extrusion of alpha-methylstyrene with both metallacycles. X-ray structural analysis of the acetone dianion complex (PMe3)4Ru((CH2)2CO) (17) was performed and displays a dihedral angle of 46-degrees-C in the metallacycle. In contrast, the 4,4-dimethyl-2-butanone dianion complex (PMe3)4Ru(CH2C(CHCMe3)O) (15) contains a flat metallacycle that is bound through the CH2 group and the oxygen atom. Reactivity studies with 15 showed that, unlike compounds 1 and 2, the organic portion remained intact upon addition of protic acids. The addition of 4,4-dimethyl-2-butanone led to a second C-C cleavage reaction, forming the di-tert-butylacetylacetonate complex (PMe3)3Ru(Me)(CH(COCH2CMe3)2) (19). Reactivity studies with 17 showed reversible formation of the isolable oxatrimethylenemethane complex 18, which was isolated and structurally characterized. Addition of acetone to 17 led to formation of mesityl oxide dianion complex (PMe3)4Ru(OC(Me)CHC(Me)CH) (19); mesityl oxide is presumably formed by aldol condensation at the metal center. Reactivity studies of the oxametallacyclobutene complex (PMe3)4Ru(OC(CMe3)CH) showed formation of free ketone upon addition of protic acids and insertion into the metal-oxygen bond upon addition of CO2. The metallacycle was converted to the silyl enol ether upon addition of trimethylsilane and to the free ketone following addition of H-2.
• A study of the silanolysis of triphenylsilane and p-methoxyphenol catalysed by (PMe3)4RuH2 and the stoichiometric reactions of (PMe3)4Ru(H)(OC6H4-p-X) (X = Me, OMe) with Ph3SiH
  作者：Melinda J. Burn、Robert G. Bergman

  DOI：10.1016/0022-328x(94)80192-4

  日期：1994.6

  The ruthenium dihydride cis-(PMe3)4Ru(H)2 (1) catalytically converts Ph3SiH and HOC6H4-p-OMe to the alcoholysis products Ph3SiOC6H4-p-OMe and H-2. This reaction was studied kinetically and the rate was found to be first-order in [1], first-order in [HOC6H4-P-OMe], and independent of [Ph3SiH]. The stoichiometric reactions of cis-(PMe3)4Ru(H)(OC6H4-p-X) (X = Me, 2; OMe, 3) with Ph3SiH were also studied in the presence of varying amounts of free para-substituted phenol. In the absence of the free phenol, compounds 2 and 3 reacted with Ph3SiH to give Ph3SiOC6H4-p-X and a compound we believe to be (PMe3)3Ru(H)3(SiPh3) (4). In the presence of large amounts of phenol (> 10 equiv.), (PMe3)4Ru(H)2 (1) was formed. However, at intermediate concentrations of free phenol, compounds 2 and 3 exhibited divergent behavior. Complex 2 gave dihydride 1 in a reaction whose rate was found to be first-order in the concentration of the starting aryloxy hydride 2, first-order in phenol and independent of [Ph3SiH]. In contrast, complex 3 reacted with less than 0.5 equiv. of p-methoxyphenol to form 1, but when approximately 1 equiv. of p-methoxyphenol was added to the solution of 3 and Ph3SiH a mixture of trihydride 4 and dihydride 1 were formed. The mechanisms of these complicated transformations, and their potential relationship to the dihydride-catalyzed silanolysis reaction, are discussed.
• Hartwig, John F.; Andersen, Richard A.; Bergman, Robert G., Organometallics, 1991, vol. 10, # 6, p. 1875 - 1887
  作者：Hartwig, John F.、Andersen, Richard A.、Bergman, Robert G.

  DOI：——

  日期：——