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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 Fukuzumi
- Issue Date
- 2011
- Journal Title
- Inorganica Chimica Acta
- ISSN
- 0020-1693
- Citation
- Inorganica Chimica Acta vol. 374, no. 1, pp. 104 - 111
- Indexed
- SCI; SCIE; SCOPUS
- Document Type
- Article
- 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
- Appears in Collections:
- 자연과학대학 > 화학·나노과학전공 > Journal papers
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