[(η6-benzene)Ru(((2,6-dimethylphenyl)NCMe)2CH)]OTf | 931119-78-7

• 英文名称: [(η6-benzene)Ru(((2,6-dimethylphenyl)NCMe)2CH)]OTf
• 英文别名: [(η6-C6H6)Ru((2,6-Me2C6H3NCMe)2CH)](O3SCF3)
• CAS: 931119-78-7
• 化学式: CF₃O₃S*C₂₇H₃₁N₂Ru
• 分子量: 633.697
• InChiKey: KUUZFLZPBBVBMF-STOPWVKLSA-M

计算性质

• 辛醇/水分配系数(LogP)：
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• 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：

  [(η6-benzene)Ru(((2,6-dimethylphenyl)NCMe)2CH)]OTf 、 氢气 以 四氢呋喃 为溶剂， 生成 [(η6-C6H6)RuH(C2H4){(2,6-Me2-C6H3NCMe)2CH2}]OTf
  参考文献：
  名称：

  Facile, Thermoreversible Cycloaddition of Small Molecules to a Ruthenium(II) Arene β-Diketiminate

  摘要：

  Formation of a vacant coordination site on a Ru center permits an unusual binding of small molecules such as ethylene, acetylene, and dihydrogen, resulting in the transformation of the chelating beta-diketiminate ligand to a beta-diimine. These representative species are observed during the catalytic hydrogenation of styrene.

  DOI：

  10.1021/om070017r
• 作为产物：
  描述：

  [(η⁶-C₆H₆)Ru(C₂H₄){(2,6-Me₂-C₆H₃NCMe)₂CH}]OTf 以 not given 为溶剂， 生成 [(η6-benzene)Ru(((2,6-dimethylphenyl)NCMe)2CH)]OTf
  参考文献：
  名称：

  Facile, Thermoreversible Cycloaddition of Small Molecules to a Ruthenium(II) Arene β-Diketiminate

  摘要：

  Formation of a vacant coordination site on a Ru center permits an unusual binding of small molecules such as ethylene, acetylene, and dihydrogen, resulting in the transformation of the chelating beta-diketiminate ligand to a beta-diimine. These representative species are observed during the catalytic hydrogenation of styrene.

  DOI：

  10.1021/om070017r

文献信息

• Comprehensive Experimental and Computational Study of η⁶-Arene Ruthenium(II) and Osmium(II) Complexes Supported by Sulfur Analogues of the β-Diketiminate Ligand
  作者：Crystal O’Connor、Darren C. Lawlor、Conor Robinson、Helge Müller-Bunz、Andrew D. Phillips

  DOI：10.1021/acs.organomet.8b00111

  日期：2018.6.25

  displaces the η6-C6H6 ligand. A comprehensive DFT study employing charge decomposition analysis (CDA) reveals a strong covalent metal–sulfur bond which dominates the metal β-thioketoiminate interaction. The M–S bond (M = Ru or Os) is strengthened by charge transfer from metal to sulfur, in contrast to the β-diketiminate species where back electron donation from the metal to the nitrogen centers is

  与β-二酮衍生物相比，一类高度开发的N，N-螯合配体，相应的β-硫酮酮酸酯，一硫代取代的类似物，仅受到了很小的关注。通过使用Lawesson试剂处理适当的β-酮亚胺可直接制备β-硫酮亚胺。采用标准合成技术为η 6 -arene的Ru（II）和Os（II）β-二亚胺基配合物，通过不同尺寸的支撑的类似系列chlorido -金属配合物的ñ -芳基取代的β-thioketoiminate配体报道。然而，带有吸电子CF 3的β-硫酮酮酸酯的金属连接小组不可能。这些络合物中的金属-氯键很容易被弱配位阴离子的各种钠盐或银盐活化，从而提供了不饱和阳离子形式的16电子物种。所有η 6 -C 6 H ^ 6金属β-thioketoiminate通过NMR和使用单晶X射线衍射技术在固体状态下进行了表征。结构研究表明，硫基的引入会在金属环内引起大量的键角变形。的反应性阳离子η 6 -C 6 H ^ 6Ru（II
• Influence of Ion Pairing on Styrene Hydrogenation Using a Cationic η⁶-Arene β-Diketiminato−Ruthenium Complex
  作者：Aitor Moreno、Paul S. Pregosin、Gábor Laurenczy、Andrew D. Phillips、Paul J. Dyson

  DOI：10.1021/om900634s

  日期：2009.11.23

  A series of salts composed of the coordinatively unsaturated ruthenium beta-diketiminato cation [(eta(6)-C6H6)Ru((ArNCMe)(2)CH)](+) (Ar = 2,6-dimethylphenyl) and different anions, i.e., OTf- (1), BF4- (2), PF6- (3), BPh4- (4), and BArF- (B((3,5-CF3)(2)C6H3)(4)(-)) (5), have been prepared and characterized. The solid state structures of 1, 2, and 5 have also been established using single-crystal X-ray diffraction, Both solution and solid state data reveal the presence of anion-cation interactions, the extent of which depends on the nature of the anion, which have been further rationalized via computed charge density profiles using DFT energy optimized models. The catalytic activity of 1-5 in the hydrogenation of styrene was found to be highly dependent on the nature of the counteranion, as inferred from investigations based on high-pressure solution NMR, pulsed gradient spin-echo (PGSE) NMR diffusion, and Overhauser NMR spectroscopy. A good correlation between catalytic activity and the extent and nature of ion pairing was found, and the structure of the active catalytic species is proposed.