(η6-C6H6)Ru(Br)(η2-(i)PrN=C(Me)N(i)Pr) | 926030-77-5

• 英文名称: (η6-C6H6)Ru(Br)(η2-(i)PrN=C(Me)N(i)Pr)
• CAS: 926030-77-5
• 化学式: C₁₄H₂₃BrN₂Ru
• 分子量: 400.324
• InChiKey: UUEGFGYGKSMYQB-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 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：

  (η6-C6H6)Ru(Br)(η2-(i)PrN=C(Me)N(i)Pr) 、 silver trifluoromethanesulfonate 以 二氯甲烷 为溶剂， 以70%的产率得到(η6-C6H6)Ru(κ1-OTf)(η2-(i)PrN=C(Me)N(i)Pr)
  参考文献：
  名称：

  Trifluoromethanesulfonate (triflate) as a moderately coordinating anion: Studies from chemistry of the cationic coordinatively unsaturated mono- and diruthenium amidinates

  摘要：

  Triflate complexes of mono- and diruthenium amidinates, (eta(6)-C6R6)Ru(kappa(1)-OTf){eta(2)-R'N=C(R")NR'} (1:R = Me; 2: R = H) and (eta(5)-C5Me5)Ru(mu-eta(2)-(PrN)-Pr-i C(Me)(NPr)-Pr-i)Ru(kappa(1)-OTf)(eta(5)-C5R5) (3:R = Me; 4: R = H), are synthesized, and coordination behavior of the triflate anion to the coordinatively unsaturated ruthenium species is investigated by crystallography and variable temperature (VT) NMR spectroscopy (F-19, H-1). The monoruthenium amidinate complexes have three-legged piano-stool structures in single crystals, which include a kappa(1)-OTf ligand with the Ru-O bond of 2.15-2.20 angstrom. In contrast, reversible dissociation of OTf is observed in variable temperature H-1 NMR spectroscopy in liquid states; the activation energy for the dissociation and recombination of the OTf ligand is varied with the substituents on the arene and amidinate ligand in the corresponding ruthenium cation and the solvent used. A typical example of moderately coordinating ability of the OTf ligand is seen in F-19 NMR spectra of (eta(6)-C6Me6)Ru(kappa(1)-OTf){eta(2)-(PrN)-Pr-i=C(Me)(NPr)-Pr-i} (1a) and (eta(6)-C6H6)Ru(kappa(1)-OTf) (eta(2)-(PrN)-Pr-i=C(Me)NPr) (2a) in CD2Cl2 at the temperature range from -90 to 20 degrees C, in which the OTf anion is dissociated in 1a, whereas 2a has a relatively robust Ru-OTf bond. Combination of crystallography and VT NMR contributes to understanding the difference in coordination behavior of the OTf ligand between two diruthenium amidinates, (eta(5)-C5Me5)Ru(mu-eta(2)-(PrN)-Pr-i=C(Me)(NPr)-Pr-i)Ru(kappa(1)-OTf)(eta(5) -C5Me5) (3) and (eta(5)-C5Me5)Ru(mu-eta(2)-(PrN)-Pr-i=C(Me)(NPr)-Pr-i)Ru(kappa(1)-OTf)(eta(5)-C5H5) (4); the results suggest that the electrondonating and sterically demanding eta(5)-C5Me5 helps for dissociation of the triflate ligand. Moderate coordinating ability of the triflate anion sometimes provides characteristic reactions of mono- and dirutheniurn amidinates which differ from the corresponding neutral halogeno-compounds or cationic coordinatively unsaturated homologues bearing fluorinated tetraarylborates; a typical example is given by inhibition of coordination of ethylene to the [(eta(6)-C6H6)Ru{eta(2)-(BuN)-Bu-t=C(Ph)(NBu)-Bu-t}](+) species by the OTf ligand. (c) 2006 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2006.08.069
• 作为产物：
  描述：

  [RuCl2(benzene)]2 、 lithium N,N'-diisopropylacetamidinate 、 lithium bromide 以 四氢呋喃 为溶剂， 以79%的产率得到(η6-C6H6)Ru(Br)(η2-(i)PrN=C(Me)N(i)Pr)
  参考文献：
  名称：

  Trifluoromethanesulfonate (triflate) as a moderately coordinating anion: Studies from chemistry of the cationic coordinatively unsaturated mono- and diruthenium amidinates

  摘要：

  Triflate complexes of mono- and diruthenium amidinates, (eta(6)-C6R6)Ru(kappa(1)-OTf){eta(2)-R'N=C(R")NR'} (1:R = Me; 2: R = H) and (eta(5)-C5Me5)Ru(mu-eta(2)-(PrN)-Pr-i C(Me)(NPr)-Pr-i)Ru(kappa(1)-OTf)(eta(5)-C5R5) (3:R = Me; 4: R = H), are synthesized, and coordination behavior of the triflate anion to the coordinatively unsaturated ruthenium species is investigated by crystallography and variable temperature (VT) NMR spectroscopy (F-19, H-1). The monoruthenium amidinate complexes have three-legged piano-stool structures in single crystals, which include a kappa(1)-OTf ligand with the Ru-O bond of 2.15-2.20 angstrom. In contrast, reversible dissociation of OTf is observed in variable temperature H-1 NMR spectroscopy in liquid states; the activation energy for the dissociation and recombination of the OTf ligand is varied with the substituents on the arene and amidinate ligand in the corresponding ruthenium cation and the solvent used. A typical example of moderately coordinating ability of the OTf ligand is seen in F-19 NMR spectra of (eta(6)-C6Me6)Ru(kappa(1)-OTf){eta(2)-(PrN)-Pr-i=C(Me)(NPr)-Pr-i} (1a) and (eta(6)-C6H6)Ru(kappa(1)-OTf) (eta(2)-(PrN)-Pr-i=C(Me)NPr) (2a) in CD2Cl2 at the temperature range from -90 to 20 degrees C, in which the OTf anion is dissociated in 1a, whereas 2a has a relatively robust Ru-OTf bond. Combination of crystallography and VT NMR contributes to understanding the difference in coordination behavior of the OTf ligand between two diruthenium amidinates, (eta(5)-C5Me5)Ru(mu-eta(2)-(PrN)-Pr-i=C(Me)(NPr)-Pr-i)Ru(kappa(1)-OTf)(eta(5) -C5Me5) (3) and (eta(5)-C5Me5)Ru(mu-eta(2)-(PrN)-Pr-i=C(Me)(NPr)-Pr-i)Ru(kappa(1)-OTf)(eta(5)-C5H5) (4); the results suggest that the electrondonating and sterically demanding eta(5)-C5Me5 helps for dissociation of the triflate ligand. Moderate coordinating ability of the triflate anion sometimes provides characteristic reactions of mono- and dirutheniurn amidinates which differ from the corresponding neutral halogeno-compounds or cationic coordinatively unsaturated homologues bearing fluorinated tetraarylborates; a typical example is given by inhibition of coordination of ethylene to the [(eta(6)-C6H6)Ru{eta(2)-(BuN)-Bu-t=C(Ph)(NBu)-Bu-t}](+) species by the OTf ligand. (c) 2006 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2006.08.069