Cyclohexa-1,3-diene;1,2,3,4,5,6-hexamethylbenzene;ruthenium | 67421-01-6

• 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: Cyclohexa-1,3-diene;1,2,3,4,5,6-hexamethylbenzene;ruthenium
• CAS: 67421-01-6
• 化学式: C₁₈H₂₆Ru
• 分子量: 343.474
• InChiKey: ZJOPGOMMFUHJAI-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.43
• 重原子数：
  19
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.44
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  Cyclohexa-1,3-diene;1,2,3,4,5,6-hexamethylbenzene;ruthenium 在 盐酸 作用下， 以 not given 为溶剂， 生成 [RuCl2(hexamethylbenzene)]2
  参考文献：
  名称：

  苯选择性还原成环己烯

  摘要：

  上的双阳离子氢化物攻击η 6 -苯复合物给出η 4 -cyclohexadiene，它与酸产率环己烯; 在苯的存在下，初始η 6 -苯复合物可以再生和循环确定。

  DOI：

  10.1039/c39820000379
• 作为产物：
  描述：

  在 [(CH₃OCH₂CH₂O)2AlH₂]Na 作用下， 以 甲苯 为溶剂， 以71%的产率得到Cyclohexa-1,3-diene;1,2,3,4,5,6-hexamethylbenzene;ruthenium
  参考文献：
  名称：

  选择性还原苯由铂金属络合物介导的环己烯的：X的射线晶体结构[（η 5 -C 5我5）IR（η 5 -C 6 ħ 6 CH 2 NO 2）] [BF 4 ]

  摘要：

  的双阳离子η 6 -苯络合物[（C Ñ我Ñ）M（C 6 H ^ 6）] 2+ [M = RH，Ñ = 5（图2a）; M = Ir，n = 5（2b）；M = RU，Ñ = 6（2C）]是通过硼氢化还原为η 5 -cyclohexadienyl配合物[（C Ñ我Ñ）M（C 6 H ^ 7）] +（3），其被进一步降低到η 4 -环己二烯络合物[（C n Me n）M（C 6 H 8）]（4）。配合物（4）与酸反应得到具有100％选择性的环己烯；当用四氟硼酸在苯中进行反应时，初始的苯配合物（2）被再生。整个反应包括添加两个氢化物，然后添加两个质子至配位的苯，并且可以构建铂金属中的循环催化器。苯全部还原为环己烯的效率按Ir> Ru> Rh的顺序降低。将反应与由铑，铱和三氯化钌水合物和四氢硼酸盐在乙醇中介导的苯还原为环己烷进行比较。其他亲核试剂也攻击（2b）中的苯环：包括甲基锂（产生两个二甲基环

  DOI：

  10.1039/dt9840001747

文献信息

• Protonation of diene complexes of rhodium, iridium, ruthenium, and osmium: a fine balance between terminal and agostic hydrides
  作者：Martin A. Bennett、Ian J. McMahon、Simon Pelling、Maurice Brookhart、David M. Lincoln

  DOI：10.1021/om00037a028

  日期：1992.1

  The structures of the cationic hydrido complexes formed on addition of HPF6 to (eta(5)-pentamethylcyclopentadienyl)- and (eta(6)-arene)metal complexes containing various 1,3-dienes or 1,5-cyclooctadiene have been investigated by IR and NMR (1-H, C-13) spectroscopy. The rhodium complexes [RhH(eta-C5Me5)(diene)]+ (diene = 1,3-cyclohexadiene (1), 2,3-dimethylbutadiene (3)) are highly fluxional eta(3)-enyl complexes with a M-H-C interaction (agostic hydrides), as shown by their H-1 and C-13 NMR spectra at -100-degrees-C and by deuteration experiments. As with other compounds of this class, two reversible processes can be observed by variable-temperature NMR spectroscopy: (1) M-H bond cleavage to give a 16e eta(3)-enyl complex, which leads to exchange of the endo C-H bonds of 1 and exchange of the agostic methyl hydrogen atoms of 3; (2) C-H bond cleavage to give a diene metal hydride, which, in combination with process 1, averages separately the endo and exo protons of 1 and the five dienyl protons of 3. The free energy of activation DELTA-G double-ended dagger for process 2 is slightly larger than for process 1, the estimated values being about 9.0 and 7.5 kcal/mol in the case of 3. The complexes [IrH(eta-C5Me5)(diene)]+ (diene = 1,3-cyclohexadiene (2), 2,3-dimethylbutadiene (4)) and [OsH(eta-arene)(diene)]+ (arene = C6H6, diene = 1,3-cyclohexadiene (5), 2,3-dimethylbutadiene (7); arene = 1,3,5-C6H3Me3, diene = 1,3-cyclohexadiene (6), 2,3-dimethylbutadiene (8)) are terminal hydrides in which the hydride ligand migrates between metal and diene reversibly and rapidly on the NMR time scale above room temperature (DELTA-G double-ended dagger congruent-to 12 kcal/mol for 2 and 4). The coupled C-13 NMR spectrum of [RuH(eta-C6H6)(C6H8)]+ (9) at -100-degrees-C suggests that this compound contains an agostic hydride similar to 1 and 3, but the H-1 and C-13 NMR spectra above -100-degrees-C resemble those expected for a highly fluxional terminal hydrido diene complex, the free energy of activation DELTA-G double-ended dagger for reversible Ru-H bond cleavage being 8.8 kcal/mol. In contrast to the rhodium complexes and most other agostic hydrides formed from protonation of diene complexes, therefore, DELTA-G double-ended dagger for C-H bonds cleavage (process 2) in 9 is less than that for M-H bond cleavage (process 1) and is probably about 5-6 kcal/mol. The compounds [RuH(eta-C6Me6)(C6Me6)]+ (10) and [RuH(eta-arene)(1,3-diene)]+ (diene = 2,3-dimethylbutadiene, arene = C6H6 (11), C6H3Me3 (12), C6Me6 (13); arene = C6Me6, diene = isoprene (14), 2-methyl-1,3-pentadiene (15), 3-methyl-1,3-pentadiene (16)) are also agostic, but in most cases limiting spectra cannot be obtained, even for process 1, at -100-degrees-C. Protonation of M(eta-arene)(1,5-COD) gives terminal hydrido diene complexes [MH(eta-arene)(1,5-COD)]+ (M = Ru, arene = C6H6, 1,3,5-C6H3Me3, C6Me6; M = Os, arene = C6H6, C6H3Me3). The compound obtained from Ru(eta-C6Me6)(1,5-COD) and DPF6 incorporates deuterium at the methylene carbon atoms of the coordinated diene, which implies that [RuH(eta-C6Me6)(1,5-COD)]+ is in equilibrium with eta(1), eta(2)-cyclooctenyl and possibly agostic eta(3)-cyclooctenyl species.All the protonated diene complexes except [OsH(eta-arene)(1,5-COD)]+ react with 2e-donor ligands (L) to give nonfluxional 18e complexes of the type [M(eta-C5Me5)(eta(3)-enyl)(L)]+ (M = Rh, Ir; L = t-BuNC) and [M'(eta-arene)(eta(3)-enyl)(L)]+ [M' = Ru, Os; L = CO, t-BuNC, P(OMe)3 (not all possible combinations)].