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Trans- and cis-Ru(II) aminophosphine complexes: Syntheses, X-ray structures and catalytic activity in transfer hydrogenation of acetophenone derivatives

机译:反式和顺式-Ru(II)氨基膦配合物:苯乙酮衍生物转移氢化中的合成,X射线结构和催化活性

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摘要

The ability of transition metal catalysts to add or remove hydrogen from organic substrates by transfer hydrogenation process is a valuable synthetic tool. For this aim, a novel Ru(II) complex with the P-N ligand [(Ph _2P)_2NCH_2-C_4H_3S] derived from thiophene-2-methylamine was synthesized starting with the complex [Ru(η6-p-cymene)(μ-Cl)Cl]2 and isolated in two isomeric forms: trans- and cis-[Ru((PPh_2)_2NCH _2-C_4H_3S)_2Cl_2], _2 and 3, respectively. The structures of both isomers were also determined by single crystal X-ray diffraction. The cis-isomer 3 can be isolated from the solution of major trans-isomer 2 as yellow crystals. However, upon dissolution 3 is rapidly converted to the trans-isomer 2. The new ruthenium(II) complex provides high catalytic activity in the transfer hydrogenation of acetophenone derivatives to 1-phenylethanol derivatives in the presence of 2-propanol as the hydrogen source. This transfer hydrogenation is characterized by low reversibility under the experimental conditions.
机译:过渡金属催化剂通过转移氢化过程从有机底物中添加或去除氢的能力是一种有价值的合成工具。为此,从配合物[Ru(η6-p-cymene)(μ-Cl)开始,合成了一种新的Ru(II)配合物,该配合物由噻吩-2-甲基胺衍生而来,具有PN配体[(Ph _2P)_2NCH_2-C_4H_3S]。 )Cl] 2并分离为两种异构形式:反式和顺式[Ru((PPh_2)_2NCH _2-C_4H_3S)_2Cl_2],_ 2和3。两种异构体的结构也通过单晶X射线衍射测定。可以从主要反式异构体2的溶液中分离出黄色晶体形式的顺式异构体3。但是,溶解后3迅速转变为反式异构体2。在以2-丙醇为氢源的情况下,新的钌(II)络合物在将苯乙酮衍生物氢化成1-苯基乙醇衍生物的过程中具有很高的催化活性。该转移氢化的特征在于在实验条件下的低可逆性。

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