(pentamethyl-η5-cyclopentadienyl)(η6-benzene)ruthenium trifluoromethanesulfonate

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机磺酸及其衍生物
• 英文名称: (pentamethyl-η5-cyclopentadienyl)(η6-benzene)ruthenium trifluoromethanesulfonate
• 英文别名: {η5-pentamethylcyclopentadienyl(ruthenium)(η6-C6H6)}(CF3SO3)
• 化学式: CF₃O₃S*C₁₆H₂₁Ru
• 分子量: 463.483
• InChiKey: MEZGSDQZFOHRLZ-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  5.0
• 重原子数：
  25
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.35
• 拓扑面积：
  65.6
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  (pentamethyl-η5-cyclopentadienyl)(η6-benzene)ruthenium trifluoromethanesulfonate 在 二氯甲烷 作用下， 以 neat (no solvent) 为溶剂， 以60%的产率得到{(C5Me5Ru)3(μ-Cl)3(μ3-CH)}(CF3SO3)
  参考文献：
  名称：

  Selective activation of carbonchlorine bonds by the electrophilic fragment “Cp★Ru+”

  摘要：

  The "Cp*Ru+" fragment (1) reacts with cyclic chlorinated hydrocarbons C6H11Cl, 1,2-C6H10Cl2, alpha-C6H6Cl6 and 1.2-C6H9(O)Cl to yield [Cp*Ru(eta-6-C6H6)](CF3SO3) (2) in 60, 90, 35 and 90% yield. respectively; with 2,2,6,6-C6H7Cl4OH the reaction depends upon the conditions but in the absence of dihydrogen [Cp*Ru(eta-6-C6H5OH)](CF3SO3) (4) is the major product. indicating a selectivity for C-Cl activation in the presence of C-O bonds; finally a new series of chlorinated clusters [(Cp*Ru)3(mu-Cl)2(mu-X)(mu-3-CY)](CF3SO3)n (X = Cl, Y = H, n = 1; 5; X = CO, Y = H. n = 2: 6; X = CO, Y = Cl, n = 2: 8) is prepared in high yield from reactions of 1 with CH2Cl2 or 1,2-C6H10Cl(OH).

  DOI：

  10.1016/0022-328x(92)80162-q
• 作为产物：
  描述：

  (C5Me5)ruthenium(1+) 、 氯代环己烷 在 氢气 作用下， 以 二氯甲烷 为溶剂， 以60%的产率得到(pentamethyl-η5-cyclopentadienyl)(η6-benzene)ruthenium trifluoromethanesulfonate
  参考文献：
  名称：

  Selective activation of carbonchlorine bonds by the electrophilic fragment “Cp★Ru+”

  摘要：

  The "Cp*Ru+" fragment (1) reacts with cyclic chlorinated hydrocarbons C6H11Cl, 1,2-C6H10Cl2, alpha-C6H6Cl6 and 1.2-C6H9(O)Cl to yield [Cp*Ru(eta-6-C6H6)](CF3SO3) (2) in 60, 90, 35 and 90% yield. respectively; with 2,2,6,6-C6H7Cl4OH the reaction depends upon the conditions but in the absence of dihydrogen [Cp*Ru(eta-6-C6H5OH)](CF3SO3) (4) is the major product. indicating a selectivity for C-Cl activation in the presence of C-O bonds; finally a new series of chlorinated clusters [(Cp*Ru)3(mu-Cl)2(mu-X)(mu-3-CY)](CF3SO3)n (X = Cl, Y = H, n = 1; 5; X = CO, Y = H. n = 2: 6; X = CO, Y = Cl, n = 2: 8) is prepared in high yield from reactions of 1 with CH2Cl2 or 1,2-C6H10Cl(OH).

  DOI：

  10.1016/0022-328x(92)80162-q

文献信息

• The Mechanism of Carbon−Carbon Bond Activation in Cationic 6-Alkylcyclohexadienyl Ruthenium Hydride Complexes
  作者：Christina M. Older、Jeffrey M. Stryker

  DOI：10.1021/ja992987e

  日期：2000.3.1

  exadienyl ruthenium hydride complexes has been investigated. Contrary to expectations, it is the 6-exo-methyl complex and not the stereoisomeric 6-endo-methyl complex that undergoes selective carbon−carbon bond activation under exceptionally mild conditions, quantitatively converting the 6-exo-methyl substituent and the hydride ligand to methane. The mechanism of the activation reaction involves dissociation

  已经研究了阳离子 6-内-甲基-η5-环己二烯基和 6-外-甲基-η5-环己二烯基氢化钌配合物中的碳-碳键活化。与预期相反，是 6-外-甲基复合物，而不是立体异构的 6-内-甲基复合物，在异常温和的条件下进行选择性碳-碳键活化，将 6-外-甲基取代基和氢化物配体定量转化为甲烷。活化反应的机制涉及通过与弱碱（通常是水）反应，质子酸从激动剂起始复合物中解离，然后在亲核金属中心的“背面”辅助下对烷基进行质子化活化。在相同条件下，相应的6-内甲基异构体发生选择性脱氢而不是脱甲基，尽管内甲基取代基靠近金属中心。对于外型和内型异构体，阳离子氢化钌中间体被确定...
• Carbon-hydrogen, carbon-oxygen, and carbon-carbon bond activation by an electrophilic ruthenium complex
  作者：Deyanira Rondon、Bruno Chaudret、Xiao Dong He、Daniel Labroue

  DOI：10.1021/ja00015a022

  日期：1991.7

  The «Cp*Ru + » fragment generated by protonation of [Cp*Ru(OMe)] 2 with CF 3 SO 3 H reacts in CH 2 Cl 2 or THF with cyclic C 6 alkenes, dienes, alcohols, ketones, enones, and diones to yield coordinated aromatic derivatives after C-H, C-O, or C-C activation. The following transformations have been performed: cyclohexene and methylcyclohexene into benzene and toluene; 1,3- or 1,5-cyclooctadiene into

  通过 [Cp*Ru(OMe)] 2 与 CF 3 SO 3 H 质子化生成的 «Cp*Ru + » 片段在 CH 2 Cl 2 或 THF 中与环状 C 6 烯烃、二烯、醇、酮、烯酮和二酮在 CH、CO 或 CC 活化后产生配位的芳族衍生物。进行了以下转化：环己烯和甲基环己烯转化为苯和甲苯；1,3-或1,5-环辛二烯转化为1,3,5-环辛三烯；环己醇、环己酮或环己烯酮转化为苯甲基环己烯酮转化为甲苯；环己二酮转化为苯酚；4,4-二甲基环己烯酮和异佛尔酮转化为4-甲基苯酚和3,5-二甲基苯酚
• Regiospecific Cp★Ru+ mediated codimerization of conjugated dienes with non-conjugated 1,5-dienes and its application to catalytic cooligomerization
  作者：Katsuyuki Masuda、Hironobu Ohkita、Shigeru Kurumatani、Kenji Itoh

  DOI：10.1016/0022-328x(93)83257-v

  日期：1993.7

  5-hexadiene complex of cationic ruthenium was obtained by regiospecific C4 homologation at the internal carbon atom of the non-conjugated diene. This stoichiometric CC bonding was extended to the catalytic codimerization and stepwise oligomerization of butadiene with 1,5-hexadiene or 1-hexene.

  当的Cp★的RuCl（η 4 -丁二烯）（1 ;其中Cp★η 5 -C 5我5）在等于或低于环境温度下用在三氟甲磺酸银（的AgOTf）存在过量的1,5-己二烯的后处理，通过在非共轭二烯的内部碳原子上的区域特异性C4同系物获得阳离子钌的2-（3'-丁烯基）-1,5-己二烯络合物。这种化学计量的CC键扩展到丁二烯与1，5-己二烯或1-己烯的催化共聚和逐步低聚。
• Stoicheiometric dehydrogenation of cyclic alkenes without hydrogen acceptors using the ‘(C₅Me₅)Ru⁺’ fragment. X-Ray crystal structure of [(η⁵-C₅Me₅)Ru-(µ₂, η⁵, η⁵-C₅Me₄OH)-Ru(η⁵-C₅Me₅)]CF₃SO₃·CH₂Cl₂
  作者：Bruno Chaudret、Françoise Dahan、Xiao Dong He

  DOI：10.1039/c39900001111

  日期：——

  The reaction of [(C5Me5)Ru(OMe)]2(2) with CF3SO3H in the presence of cyclic alkenes (cyclohexene or 4-methylcyclohexene) affords the π-arena derivatives [(C5Me5)Ru(η6-C6H6)]CF3SO3(4) and [(C5Me5)Ru(η6-C5H5Me)](CF3SO3)(5) in 40–60% isolated yield (100% spectroscopic yield) while the same reaction with tetramethylcyclopentenone affords the novel triple-decker title complex (3) in 90% yield; a mechanism involving unstable dihydrogen intermediate complexes is proposed.

  在环烯（环己烯或 4-甲基环己烯）存在下，[(C5Me5)Ru(OMe)]2(2) 与 CF3SO3H 反应可生成 Ï-arena 衍生物 [(C5Me5)Ru(δ-6-C6H6)]CF3SO3(4) 和 [(C5Me5)Ru(δ-6-C5H5Me)](CF3SO3)(5)，分离收率为 40%-60%（光谱收率为 100%）；提出了一种涉及不稳定二氢中间络合物的机理。
• Molecular engineering of solid-state materials: organometallic building blocks
  作者：Paul J. Fagan、Michael D. Ward、Joseph C. Calabrese

  DOI：10.1021/ja00187a024

  日期：1989.3