Please use this identifier to cite or link to this item: https://doi.org/10.1002/asia.201000930
Title: Syntheses and structures of ruthenium(II) N,S-heterocyclic carbene diphosphine complexes and their catalytic activity towards transfer hydrogenation
Authors: Ding, N.
Hor, T.S.A. 
Keywords: carbenes
diphosphines
N,S-heterocycles
ruthenium
transfer hydrogenation
Issue Date: 6-Jun-2011
Citation: Ding, N., Hor, T.S.A. (2011-06-06). Syntheses and structures of ruthenium(II) N,S-heterocyclic carbene diphosphine complexes and their catalytic activity towards transfer hydrogenation. Chemistry - An Asian Journal 6 (6) : 1485-1491. ScholarBank@NUS Repository. https://doi.org/10.1002/asia.201000930
Abstract: Phosphine exchange of [RuIIBr(MeCOO)(PPh3) 2(3-RBzTh)] (3-RBzTh=3-benzylbenzothiazol-2-ylidene) with a series of diphosphines (bis(diphenylphosphino)methane (dppm), 1,2-bis(diphenylphosphino) ethylene (dppv), 1,1′-bis(diphenylphosphino)ferrocene (dppf), 1,4-bis(diphenylphosphino)butane (dppb), and 1,3-(diphenylphosphino)propane (dppp)) gave mononuclear and neutral octahedral complexes [RuBr(MeCOO) (η2-P2)(3-RBzTh)] (P2=dppm (2), dppv (3), dppf (4), dppb (5), or dppp (6)), the coordination spheres of which contained four different ligands, namely, a chelating diphosphine, carboxylate, N,S-heterocyclic carbene (NSHC), and a bromide. Two geometric isomers of 6 (6 a and 6 b) have been isolated. The structures of these products, which have been elucidated by single-crystal X-ray crystallography, show two structural types, I and II, depending on the relative dispositions of the ligands. Type I structures contain a carbenic carbon atom trans to the oxygen atom, whereas two phosphorus atoms are trans to bromine and oxygen atoms. The type II system comprises a carbene carbon atom trans to one of the phosphorus atoms, whereas the other phosphorus is trans to the oxygen atom, with the bromine trans to the remaining oxygen atom. Complexes 2, 3, 4, and 6 a belong to type I, whereas 5 and 6 b are of type II. The kinetic product 6 b eventually converts into 6 a upon standing. These complexes are active towards catalytic reduction of para-methyl acetophenone by 2-propanol at 82 °C under 1 % catalyst load giving the corresponding alcohols. The dppm complex 2 shows the good yields (91-97 %) towards selected ketones. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Source Title: Chemistry - An Asian Journal
URI: http://scholarbank.nus.edu.sg/handle/10635/95014
ISSN: 18614728
DOI: 10.1002/asia.201000930
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