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Cooperative catalysis of a trinuclear ruthenium(II) complex in transfer hydrogenation of ketones by formic acid

Title
Cooperative catalysis of a trinuclear ruthenium(II) complex in transfer hydrogenation of ketones by formic acid
Authors
Yano Y.Kojima T.Fukuzumi S.
Ewha Authors
Shunichi Fukuzumi
SCOPUS Author ID
Shunichi Fukuzumiscopus
Issue Date
2011
Journal Title
Inorganica Chimica Acta
ISSN
0020-1693JCR Link
Citation
vol. 374, no. 1, pp. 104 - 111
Indexed
SCI; SCIE; SCOPUS WOS scopus
Abstract
A novel TPA derivative (TPA = tris(2-pyridylmethyl)amine) having two 1,10-phenanthroline (phen) moieties via amide linkage was synthesized and this ligand reacted with [Ru(hmb)Cl 2] 2 (hmb: hexamethylbenzene) to give a trinuclear Ru(II) complex, [RuCl(TPA-{phenRuCl(hmb)} 2-H +)](PF 6) 2 (1-Cl), in a moderate yield. The complex involves a deprotonated and oxygen-coordinated amide linkage, which exhibits reversible protonation-deprotonation equilibrium. The chlorido complex was converted to be an aqua complex, [Ru(H 2O)(TPA- {phenRu(H 2O) 2(hmb)} 2-H +)](SO 4) 5/2 (1-H 2O), by the reaction of 1-Cl with Ag 2SO 4 in H 2O. Transfer hydrogenation of ketones was examined by using 1-Cl as a catalyst and HCOONa as a hydride source in H 2O/CH 3OH (1:1 v/v) at 50 °C under Ar. The time-course of the transfer hydrogenation of cyclohexanone to give cyclohexanol revealed that 1-Cl showed a cooperative effect on the catalytic reactivity as compared with that of mononuclear [RuCl(hmb)(phen)] (3-Cl) and [RuCl((1-Naph) 2-TPA)]PF 6 in H 2O/CH 3OH (1:2 v/v) under the same conditions. The detailed kinetic study has revealed that the catalytic transfer hydrogenation proceeds via the formato complex, which interacts with a substrate rather than via the hydrido complex. The two Ru centers placed at close proximity in 1-H 2O enhanced the interaction of the formato complex with a substrate, resulting in an increase in the catalytic reactivity as compared with the mononuclear complex. © 2011 Elsevier B.V. All rights reserved.
DOI
10.1016/j.ica.2011.01.100
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자연과학대학 > 화학·나노과학전공 > Journal papers
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