Université de Lyon, Institut de Chimie de Lyon, UMR CNRS-Université de Lyon 1-ESCPE Lyon, Equipe Chimie Organométallique de Surface, Villeurbanne, France.
Dalton Trans. 2012 Dec 7;41(45):13919-26. doi: 10.1039/c2dt31644g. Epub 2012 Oct 1.
Suspensions of small sized (1-2.5 nm) ruthenium nanoparticles (RuNPs) have been obtained by decomposition, under H(2), of (η(4)-1,5-cyclooctadiene)(η(6)-1,3,5-cyclooctatriene)ruthenium(0), [Ru(COD)(COT)], in the ionic liquid 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, [C(1)C(4)Im][NTf(2)], and in the presence of different compounds acting as ligands: C(8)H(17)NH(2), PPhH(2), PPh(2)H and H(2)O. Previous and new liquid NMR experiments showed that the ligands are coordinated or in the proximity to the surface of the RuNPs. Herein is reported how the ligand affects the catalytic performance (activity and selectivity) compared to a ligand-free system of RuNPs, when RuNPs in [C(1)C(4)Im][NTf(2)] are used as catalysts for the hydrogenation of various unsaturated compounds (1,3-cyclohexadiene, limonene and styrene). It has been observed that σ-donor ligands increase the activity of the nanoparticles, contrarily to π-acceptor ones.
已通过在氢气下分解（η(4)-1,5-环辛二烯）（η(6)-1,3,5-环辛三烯）钌(0)，[Ru(COD)(COT)]，来获得 1-2.5nm 尺寸的小尺寸钌纳米颗粒（RuNPs）的悬浮液，其中[Ru(COD)(COT)]在离子液体 1-丁基-3-甲基咪唑双（三氟甲烷磺酰基）亚胺，[C(1)C(4)Im][NTf(2)]，中存在，并且存在不同的化合物作为配体：C(8)H(17)NH(2)，PPhH(2)，PPh(2)H 和 H(2)O。之前和新的液体 NMR 实验表明，配体与 RuNPs 的表面配位或靠近 RuNPs 的表面。本文报道了在[C(1)C(4)Im][NTf(2)]中使用 RuNPs 作为各种不饱和化合物（1,3-环己二烯，柠檬烯和苯乙烯）加氢的催化剂时，与无配体的 RuNPs 系统相比，配体如何影响催化性能（活性和选择性）。已经观察到σ-供体配体增加了纳米颗粒的活性，而π-受体配体则相反。
