Ru(η(6)-hexamethylbenzene)(η(4)-1,5-cyclooctadiene) | 71896-91-8

• 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: Ru(η(6)-hexamethylbenzene)(η(4)-1,5-cyclooctadiene)
• 英文别名: (η6-hexamethylbenzene)(η4-1,5-cyclooctadiene)ruthenium(0)；(1Z,5Z)-cycloocta-1,5-diene;1,2,3,4,5,6-hexamethylbenzene;ruthenium
• CAS: 71896-91-8
• 化学式: C₂₀H₃₀Ru
• 分子量: 371.528
• InChiKey: KPGGSVWHIYMTTD-GHDUESPLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.21
• 重原子数：
  21
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.5
• 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：

  hexafluorophosphoric acid 、 Ru(η(6)-hexamethylbenzene)(η(4)-1,5-cyclooctadiene) 以 乙醚 为溶剂， 生成 {(η6-hexamethylbenzene)(η4-1,5-cyclooctadiene)hydridoruthenium(II)}hexafluorophosphate
  参考文献：
  名称：

  铑，铱，钌和的二烯配合物的质子化：末端氢化物与过失氢化物之间的良好平衡

  摘要：

  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)].

  DOI：

  10.1021/om00037a028
• 作为产物：
  描述：

  {(η6-hexamethylbenzene)(η4-1,5-cyclooctadiene)hydridoruthenium(II)}hexafluorophosphate 在 sodium carbonate 作用下， 以 水 为溶剂， 以80%的产率得到Ru(η(6)-hexamethylbenzene)(η(4)-1,5-cyclooctadiene)
  参考文献：
  名称：

  铑，铱，钌和的二烯配合物的质子化：末端氢化物与过失氢化物之间的良好平衡

  摘要：

  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)].

  DOI：

  10.1021/om00037a028
• 作为试剂：
  描述：

  二烯丙基丙二酸二甲酯 在 Ru(η(6)-hexamethylbenzene)(η(4)-1,5-cyclooctadiene) 作用下， 以 1,2-二氯乙烷 为溶剂， 反应 24.0h， 以99%的产率得到3-methyl-4-methylene-cyclopentane-1,1-dicarboxylic acid dimethyl ester
  参考文献：
  名称：

  Ruthenium(II)-Catalyzed Isomer-Selective Cyclization of 1,6-Dienes Leading to exo-Methylenecyclopentanes:  Unprecedented Cycloisomerization Mechanism Involving Ruthenacyclopentane(hydrido) Intermediate

  摘要：

  In the presence of a catalytic amount of ruthenium(II) complexes, [RuCl2(cod)](n), RuCl2(cod)(MeCN)(2), [RuCl2(nbd)](n). [RuCl2(CO)(3)](2), and Cp*Ru(cod)Cl, 1,6-dienes were effectively converted into the corresponding exo-methylenecyclopentanes in good to excellent yields with good isomer purity in i-PrOH at 90 degreesC. The alcoholic solvent was essential for the present catalytic cyclization, and the efficiency increased in the following order: t-BuOH << EtOH less than or equal to i-PrOH. In contrast, a Ru(0) complex. (C6Me6)Ru(cod), catalyzed the cycloisomerization only in 1,2-dichloroethane. The unusual isomer-selectivity occurred when a 1,7-octadiene was subjected to cyclization to give a similar exo-methylenecyclopentane isomer as the major product. The identical isomer selectivity was observed for the cyclization of unsymmetrical 1,6-dienes having one terminal- and one internal-alkene termini. On the basis of the results from the studies using the known ruthenium hydrides and deuterium-labeling substrates, the novel mechanism via the Ru(II) <--> Ru(IV) system involving a ruthenacyclopentane(hydrido) intermediate was proposed, which better explains the particular regiochemistry of the present cyclization than other previous mechanisms.

  DOI：

  10.1021/ja010134s

文献信息

• Stoichiometric alkyne cyclotrimerization at a ruthenium centre: A new synthetic route to Ru(η6-arene)(η4-cycloocta-1,5-diene) complexes
  作者：Paolo Pertici、Alessandra Verrazzani、Giovanni Vitulli、Richard Baldwin、Martin A. Bennett

  DOI：10.1016/s0022-328x(97)00425-7

  日期：1998.1

  Alkynes RC2R' [R = H, R' = Bu-n, CH2CMeEt, (CH2)(5)C2H; R = R' = Me, Ph; R = Me, R' = Pr-n] undergo stoichiometric cyclotrimerization on reaction with the naphthalene-ruthenium(0) complex Ru(eta(6)-C10H8)(eta(4)-C8H12), 1, at room temperature to give the corresponding Ru(eta(6)-arene)(eta 4-C8H12) complexes in moderate to excellent yield. Unsymmetrical alkynes give a mixture of the isomeric eta(6)-1,3,5-(a) and eta(6)-1,2,4-arene (b) complexes, the ratio a:b being dependent on the electronic and steric effects of R and R'. In the presence of 1, 1-hexyne and 4-methyl-1-hexyne cocyclotrimerize with acetonitrile to give substituted pyridines, which are formed in addition to the Ru(eta(6)-arene)(eta(4)-C8H12) complexes. (C) 1998 Elsevier Science S.A.