(η5-C5Me5)Ru(μ2-(i)PrN=C(Me)N(i)Pr)Ru(Br)(η5-C5Me5) | 326803-05-8

• 分子结构分类: 有机化合物
• 英文名称: (η5-C5Me5)Ru(μ2-(i)PrN=C(Me)N(i)Pr)Ru(Br)(η5-C5Me5)
• 英文别名: [(η5-C5Me5)Ru(μ2-(i)PrNC(Me)=N(i)Pr)Ru(Br)(η5-C5Me5)]；bromoruthenium(1+);(C-methyl-N-propan-2-ylcarbonimidoyl)-propan-2-ylazanide;1,2,3,4,5-pentamethylcyclopenta-1,3-diene;ruthenium(2+)
• CAS: 326803-05-8
• 化学式: C₂₈H₄₇BrN₂Ru₂
• 分子量: 693.739
• InChiKey: OBJCHOHTTNLJMP-UHFFFAOYSA-M

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：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
  None
• 氢给体数：
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• 氢受体数：
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反应信息

• 作为反应物：
  描述：

  六氟磷酸银 、 (η5-C5Me5)Ru(μ2-(i)PrN=C(Me)N(i)Pr)Ru(Br)(η5-C5Me5) 以 二氯甲烷 为溶剂， 以95%的产率得到[(η5-C5Me5)Ru(μ2-(i)PrNC(Me)=N(i)Pr)Ru(η5-C5Me5)]PF6
  参考文献：
  名称：

  Novel Coordinatively Unsaturated Bimetallic Complexes, [(η⁵-C₅Me₅)Ru(μ₂-ⁱPrNC(Me)NⁱPr)Ru(η⁵-C₅Me₅)]⁺:  A Bridging Amidinate Ligand Perpendicular to the Metal−Metal Axis Effectively Stabilizes the Highly Reactive Cationic Diruthenium Species

  摘要：

  Coordinatively unsaturated diruthenium complexes, [(eta5-C5Me5)Ru(mu2-iPrNC(Me)=NiPr)Ru(eta5-C5Me5)]+, of which crystallography revealed structures bearing a bridging amidinate ligand perpendicular to the Ru-Ru axis, were synthesized by anion exchange of [(eta5-C3Me5(Ru(mu2-iPrNC(Me)=NiPr)Ru(eta5-C5Me5)]+ Br- by weakly coordinating anions. Variable-temperature NMR showed rapid motion of the bridging amidinate ligand. The coordinatively unsaturated nature of the cationic complexes provides their high reactivity toward a series of two electron donor ligands. Oxidative addition of molecular hydrogen occurred to give [(eta5-C5Me5)Ru(mu2-iPrNC(Me)=NiPr)(mu-H)Ru(eta5-C5Me5)(H)]+, which was isolated and characterized.

  DOI：

  10.1021/ja016899h
• 作为产物：
  描述：

  lithium N,N'-diisopropylacetamidinate 、 [(η5-C5Me5)RuBr]4 以 not given 为溶剂， 以83%的产率得到(η5-C5Me5)Ru(μ2-(i)PrN=C(Me)N(i)Pr)Ru(Br)(η5-C5Me5)
  参考文献：
  名称：

  (η5-C5Me5)Ru(μ2-iPrNC(Me)NiPr)Ru(X)(η5-C5Me5)：μ2-脒基配体的一种不寻常的键合模式，为脒基的 π-共轭电子的配位能力提供了第一个明确的证据过渡金属的配体

  摘要：

  DOI：

  10.1021/ja003250o

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.