(η6-C6H6)Ru(Br)(η2-(t)BuN=C(Ph)N(t)Bu) | 470475-06-0

• 英文名称: (η6-C6H6)Ru(Br)(η2-(t)BuN=C(Ph)N(t)Bu)
• CAS: 470475-06-0
• 化学式: C₂₁H₂₉BrN₂Ru
• 分子量: 490.449
• InChiKey: HTLNDMSOPGZBTK-UHFFFAOYSA-M

反应信息

• 作为反应物：
  描述：

  (η6-C6H6)Ru(Br)(η2-(t)BuN=C(Ph)N(t)Bu) 、 氘代苯 以 1,2-二氯乙烷 为溶剂， 生成
  参考文献：
  名称：

  Access to Novel Ruthenium−Amidinate Complexes, (η⁶-arene)Ru(η²-amidinate)X and [Ru(η²-amidinate)(MeCN)₄]⁺PF₆^- by Photochemical Displacement of the Benzene Ligand in (η⁶-C₆H₆)Ru(η²-amidinate)X

  摘要：

  Novel ruthenium-amidinate complexes, (eta(6)-C6H5R)Ru(eta(2)-amidinate)X (R = Me, OMe, F) (4) and [Ru(eta(2)-amidinate)(MeCN)(4)]+PF6- (5) are synthesized by photochemical displacement of the benzene ligand in (eta(6)-C6H6)Ru(eta(2)-amidinate)X (3) by arenes or MeCN. The acetonitrile ligands of 5 are easily replaceable by other a-donor ligands (L) such as pyridines, phosphines, and isocyanides to afford the corresponding derivatives, [Ru(eta(2)-amidinate)(MeCN)(n)(L)(4-n)(+)] PF6- (n = 1 or 2).

  DOI：

  10.1021/om020227y

文献信息

• Trifluoromethanesulfonate (triflate) as a moderately coordinating anion: Studies from chemistry of the cationic coordinatively unsaturated mono- and diruthenium amidinates
  作者：Taizo Hayashida、Hideo Kondo、Jun-ichi Terasawa、Karl Kirchner、Yusuke Sunada、Hideo Nagashima

  DOI：10.1016/j.jorganchem.2006.08.069

  日期：2007.1

  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)Rueta(2)-(BuN)-Bu-t=C(Ph)(NBu)-Bu-t}](+) species by the OTf ligand. (c) 2006 Elsevier B.V. All rights reserved.