(PMe3)4Ru(η2-C6H4) | 119503-00-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (PMe3)4Ru(η2-C6H4)
• 英文别名: Ru(PMe3)4[η2-C6H4]
• CAS: 119503-00-3
• 化学式: C₁₈H₄₀P₄Ru
• 分子量: 481.481
• InChiKey: PEQQTEZMXBVPAL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.46
• 重原子数：
  23.0
• 可旋转键数：
  4.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.67
• 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：

  (PMe3)4Ru(η2-C6H4) 在 aniline 作用下， 以 苯 为溶剂， 以68.2%的产率得到Ru(PMe3)4(η2-NHC6H4)
  参考文献：
  名称：

  Hartwig, John F.; Bergman, Robert G.; Andersen, Richard A., Journal of the American Chemical Society, 1991, vol. 113, # 9, p. 3404 - 3418

  摘要：

  DOI：
• 作为产物：
  描述：

  RuCl2(PMe3)4 在 PhMgBr 作用下， 以 乙醚 为溶剂， 以35-50的产率得到(PMe3)4Ru(η2-C6H4)
  参考文献：
  名称：

  Hartwig, John F.; Bergman, Robert G.; Andersen, Richard A., Journal of the American Chemical Society, 1991, vol. 113, # 9, p. 3404 - 3418

  摘要：

  DOI：

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
• Synthesis of a highly reactive (benzyne)ruthenium complex. Carbon-carbon, carbon-hydrogen, nitrogen-hydrogen and oxygen-hydrogen activation reactions
  作者：John F. Hartwig、Richard A. Andersen、Robert G. Bergman

  DOI：10.1021/ja00189a058

  日期：1989.3

  ruthenium benzyne complex, (PMesub 3})sub 4}Ru(eta}sup 2}-Csub 6}Hsub 4}) (1). The ruthenium-carbon bond in this molecule reacts with a wide range of organic substrates that are typically inert toward late transition-metal-carbon bonds, including those in benzyne complexes. For example, complex 1 reacts cleanly with arylamine N-H bonds, water O-H bonds, and benzyl and aryl C-H bonds. It reacts with

  作者在此报告了一种异常活泼的钌苯炔配合物 (PMesub 3})sub 4}Ru(eta}sup 2}-Csub 6}Hsub 4}) (1 ）。该分子中的钌 - 碳键与范围广泛的有机底物反应，这些有机底物通常对后期过渡金属 - 碳键呈惰性，包括苯配合物中的那些。例如，配合物 1 与芳胺 NH 键、水 OH 键以及苄基和芳基 CH 键反应良好。它与苯乙酮反应产生 O 键合的烯醇复合物，干净地插入苯甲醛，并裂解丙酮的 CC 键。
• 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.; Andersen, Richard A.; Bergman, Robert G., Journal of the American Chemical Society, 1991, vol. 113, # 17, p. 6492 - 6498
  作者：Hartwig, John F.、Andersen, Richard A.、Bergman, Robert G.

  DOI：——

  日期：——