Electrogenerated polypyridyl ruthenium hydride and ligand activation for water reduction to hydrogen and acetone to iso-propanol.
نویسندگان
چکیده
The complex [Ru(tpy)(bpy)(S)](2+) (tpy = 2,2':6',2''-terpyridine, bpy = 2,2'-bipyridine, S = solvent) is an electrocatalyst for water or proton reduction to hydrogen and for reduction of acetone to iso-propanol in CH3CN. Electrocatalysis is initiated by sequential 1e(-) reductions at the tpy and bpy ligands followed by addition of water to give a ruthenium hydride intermediate. Significant rate enhancements for hydrogen evolution are observed with added weak acids, such as H2PO4(-), for the latter, with a rate enhancement of 10(4) compared to water. The reactivity of the in situ electrogenerated hydride toward hydride transfer is promoted by ligand reduction.
منابع مشابه
Experimental and Theoretical Study of CO2 Insertion into Ruthenium Hydride Complexes.
The ruthenium hydride [RuH(CNN)(dppb)] (1; CNN = 2-aminomethyl-6-tolylpyridine, dppb = 1,4-bis(diphenylphosphino)butane) reacts rapidly and irreversibly with CO2 under ambient conditions to yield the corresponding Ru formate complex 2. In contrast, the Ru hydride 1 reacts with acetone reversibly to generate the Ru isopropoxide, with the reaction free energy ΔG°(298 K) = -3.1 kcal/mol measured b...
متن کاملAqua[2-(2-pyridyl)-1,8-naphthyridine-κ2 N 1,N 2](2,2′:6′,2′′-terpyridine-κ3 N,N′,N′′)ruthenium(II) bis(hexafluoridophosphate) acetone sesquisolvate
The asymmetric unit of the title compound, [Ru(C(13)H(9)N(3))(C(15)H(11)N(3))(H(2)O)](PF(6))(2)·1.5C(3)H(6)O, consists of two crystallographically independent Ru(II) complexes. Each complex is approximately octa-hedral with the Ru(II) atom bound by an N,N'-coordinated 2-(2-pyrid-yl)-1,8-naphthyridine (pynp) ligand, a meridional 2,2':6',2''-terpyridine (tpy) ligand and one aqua ligand. The tpy l...
متن کاملPhotoinduced ligand isomerisation in a pyrazine-containing ruthenium polypyridyl complex.
Photochemically-induced ligand rearrangements for the N2 and N4 coordination isomers of the complex [Ru(bpy)(2)(Hpztr)](2+) and its deprotonated analogue [Ru(bpy)(2)(pztr)](+), where bpy is 2,2'-bipyridyl and Hpztr is pyrazine-1,2,4-triazole ligand, are reported. (1)H NMR spectroscopic and HPLC studies indicate that in acetone and acetonitrile the complexes are photostable when the triazole rin...
متن کاملHomogeneously catalysed conversion of aqueous formaldehyde to H2 and carbonate
Small organic molecules provide a promising solution for the requirement to store large amounts of hydrogen in a future hydrogen-based energy system. Herein, we report that diolefin-ruthenium complexes containing the chemically and redox non-innocent ligand trop2dad catalyse the production of H2 from formaldehyde and water in the presence of a base. The process involves the catalytic conversion...
متن کاملElectrocatalytic reduction of protons to hydrogen by a water-compatible cobalt polypyridyl platform.
A cobalt(ii) complex supported by the new tetradentate polypyridyl ligand PY4 is an electrocatalyst for the reduction of protons to hydrogen and can operate in 50% aqueous media.
متن کاملذخیره در منابع من
با ذخیره ی این منبع در منابع من، دسترسی به آن را برای استفاده های بعدی آسان تر کنید
برای دانلود متن کامل این مقاله و بیش از 32 میلیون مقاله دیگر ابتدا ثبت نام کنید
ثبت ناماگر عضو سایت هستید لطفا وارد حساب کاربری خود شوید
ورودعنوان ژورنال:
- Physical chemistry chemical physics : PCCP
دوره 15 24 شماره
صفحات -
تاریخ انتشار 2013