benzene;2,3-dimethylbuta-1,3-diene;ruthenium | 137202-84-7

• 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: benzene;2,3-dimethylbuta-1,3-diene;ruthenium
• CAS: 137202-84-7
• 化学式: C₁₂H₁₆Ru
• 分子量: 261.329
• InChiKey: ZCKCPIUTBCHCAA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
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• 可旋转键数：
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• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  benzene;2,3-dimethylbuta-1,3-diene;ruthenium 、 均三甲苯 以 neat (no solvent) 为溶剂， 生成
  参考文献：
  名称：

  （η 6 -Aren）（η 4 -丁-1,3-二烯）钌（O）-komplexe：SYNTHESE UND eigenschaften sowie kristallstruktur冯（粗苯）（丁二烯）钌

  摘要：

  （η 6 -Are）（η 4 -二烯）Ru配合物（芳烃=苯，均三甲苯，六甲基苯;二烯=丁-1,3-二烯，异戊二烯，2,3-二甲基和1,4- diphenylbuta-1，通过（芳烃）RuCl 2吡啶加合物与相应的丁烯二基镁化合物在四氢呋喃中的反应合成3-（二烯）。二烯单元不进行交换反应，而在一种情况下，苯被1，3，5-三甲基苯取代。对（C 6 H 6）（C 4 H 6）Ru的X射线衍射分析表明，短-长-短-键序列对于过渡金属丁二烯化合物而言是非常不寻常的。1 H-NMR研究证明sp 2更明显 与Fe和Ru的三羰基丁二烯配合物相比，末端二烯C原子的化学特征。

  DOI：

  10.1016/0022-328x(93)80477-s
• 作为产物：
  描述：

  [Ru(η-C6H6)Cl2(pyridine)] 在 (H₂CCMeCMeCH₂Mg*2THF)n 作用下， 以 四氢呋喃 为溶剂， 以25%的产率得到benzene;2,3-dimethylbuta-1,3-diene;ruthenium
  参考文献：
  名称：

  （η 6 -Aren）（η 4 -丁-1,3-二烯）钌（O）-komplexe：SYNTHESE UND eigenschaften sowie kristallstruktur冯（粗苯）（丁二烯）钌

  摘要：

  （η 6 -Are）（η 4 -二烯）Ru配合物（芳烃=苯，均三甲苯，六甲基苯;二烯=丁-1,3-二烯，异戊二烯，2,3-二甲基和1,4- diphenylbuta-1，通过（芳烃）RuCl 2吡啶加合物与相应的丁烯二基镁化合物在四氢呋喃中的反应合成3-（二烯）。二烯单元不进行交换反应，而在一种情况下，苯被1，3，5-三甲基苯取代。对（C 6 H 6）（C 4 H 6）Ru的X射线衍射分析表明，短-长-短-键序列对于过渡金属丁二烯化合物而言是非常不寻常的。1 H-NMR研究证明sp 2更明显 与Fe和Ru的三羰基丁二烯配合物相比，末端二烯C原子的化学特征。

  DOI：

  10.1016/0022-328x(93)80477-s

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)].