期刊
INORGANICA CHIMICA ACTA
卷 299, 期 2, 页码 155-163出版社
ELSEVIER SCIENCE SA
DOI: 10.1016/S0020-1693(99)00488-0
关键词
crystal structures; ruthenium complexes; hydride complexes; formato complexes
A novel type of hydride complex [Ru(tpy)(4,4'-X(2)bpy)H](+) (X = H and MeO) was synthesized. The stronger hydridic character of the complexes compared with [Ru(bpy)(2)(L)H](+) type complexes (L = CO, PPh3 and AsPh3) was demonstrated by the relatively high chemical shifts of Ru-H in the H-1 NMR spectra and by higher reactivities with CO2. The reactions of [Ru(tpy)(4,4'-X(2)bpy)H](+) with CO2 occurred at second-order rate constants varying from (4.69 +/- 0.02) to (5.51 +/- 0.04) x 10(-3) M-1 s(-1) depending on both solvent and X, giving the formato complexes [Ru(tpy)(4,4'-X(2)bpy)(OCHO)](+) quantitatively. The rate constant was increased with the increase of solvent acceptor number, and the reaction of [Ru(tpy){4,4'-(MeO)(2)bpy}H](+) with CO2 was found to be 3.6 times faster than that of [Ru(tpy)(bpy)H](+). These results suggest that nucleophilic attack of the hydride ligand to the carbon atom of CO2 is the rate determining step for the formation of the formato complex. The structure of the formato complex [Ru(tpy)(bpy)(OCHO)](PF6) was determined by X-ray crystallographic analysis. (C) 2000 Elsevier Science S.A. All rights reserved.
作者
我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。
推荐
暂无数据