Ruthenium, (acetato-O)chlorotetrakis(trimethylphosphine)-, (OC-6-23)- | 1187982-90-6

• 物质功能分类: 有机原料 - 羧酸类化合物及衍生物 - 羧酸酯及其衍生物
• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: Ruthenium, (acetato-O)chlorotetrakis(trimethylphosphine)-, (OC-6-23)-
• 英文别名: cis-[RuCl(CH3COO)(P(CH3)3)4]；cis-[(PMe3)4RuCl(OAc)]；cis-{Ru(O2CMe)Cl(PMe3)4}；RuCl(OAc)(PMe₃)₄
• CAS: 1187982-90-6；88968-54-1
• 化学式: C₁₄H₃₉ClO₂P₄Ru
• 分子量: 499.88
• InChiKey: PTIIOYNEBHKSKV-UHFFFAOYSA-L

物化性质

• 熔点：
  284-294°C (decomposition)

计算性质

• 辛醇/水分配系数(LogP)：
  6.13
• 重原子数：
  22.0
• 可旋转键数：
  5.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.93
• 拓扑面积：
  26.3
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  Ruthenium, (acetato-O)chlorotetrakis(trimethylphosphine)-, (OC-6-23)- 以 neat (no solvent, solid phase) 为溶剂， 以69%的产率得到fac-[(PMe3)3RuCl(η2-OAc)]
  参考文献：
  名称：

  三甲基膦钌配合物催化的二氧化碳加氢：使用高压NMR光谱的机理研究

  摘要：

  复杂的顺式-（PMe 3）4 RuCl（OAc）（1）在碱和醇助催化剂存在下，充当将CO 2加氢成甲酸的催化剂。NMR谱显示，1存在于溶液中的平衡与FAC - （PME 3）3的RuCl（η 2 -OAc）（2），[（PME 3）4的Ru（η 2 -OAc）]氯（3A），和免费的PMe 3。发现复合物2的CO 2不良加氢催化剂在催化条件下用于1。配合物3a可以通过将某些醇（例如MeOH，EtOH或C 6 H 5 OH）添加到1在CDCl 3中的溶液中来制备。的氯离子3A被交换为非配位阴离子BPH 4 -或B（氩˚F）4 -（B（AR ˚F）4 =四（3,5-双（三氟甲基）苯基）硼酸盐），以产生[（PME 3）4的Ru（η 2 -OAc）] BPH 4（图3b）和[（PME3）4的Ru（η 2 -OAc）] B（AR ˚F）4（图3c）。发现在醇助催化剂存在下，在CO 2催化加氢成甲酸中，配

  DOI：

  10.1021/om900128s

文献信息

• Hydrogenation of Carbon Dioxide Catalyzed by Ruthenium Trimethylphosphine Complexes:  The Accelerating Effect of Certain Alcohols and Amines
  作者：Pradip Munshi、A. Denise Main、John C. Linehan、Chih-Cheng Tai、Philip G. Jessop

  DOI：10.1021/ja0167856

  日期：2002.7.1

  cocatalyst and a stoichiometric amount of base are required during the hydrogenation of CO(2) to formic acid catalyzed by ruthenium trimethylphosphine complexes. Variation of the choice of alcohol and base causes wide variation in the rate of reaction. Acidic, nonbulky alcohols and triflic acid increase the rate of hydrogenation an order of magnitude above that which can be obtained with traditionally

  在由三甲基膦配合物催化的 CO(2) 加氢为甲酸的过程中，需要微量的醇助催化剂和化学计量的碱。醇和碱选择的变化导致反应速率的广泛变化。酸性、非大体积醇和三氟甲磺酸可将加氢速率提高一个数量级，高于传统使用的甲醇或水所能获得的速率。类似地，使用 DBU 而不是 NEt(3) 将反应速率提高一个数量级。现在已经获得了高达 95,000 h(-1) 的周转频率，并且使用此处确定的助催化剂和胺组合应该可以实现更高的速率。描述了初步的原位 NMR 光谱观察，并讨论了醇和碱的可能作用。
• 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.
• Hartwig, John F.; Bergman, Robert G.; Andersen, Richard A., Journal of the American Chemical Society, 1991, vol. 113, # 18, p. 6499 - 6508
  作者：Hartwig, John F.、Bergman, Robert G.、Andersen, Richard A.

  DOI：——

  日期：——
• Hartwig, John F.; Bergman, Robert G.; Andersen, Richard A., Organometallics, 1991, vol. 10, # 9, p. 3326 - 3344
  作者：Hartwig, John F.、Bergman, Robert G.、Andersen, Richard A.

  DOI：——

  日期：——