Design, Identification, and Evolution of a Surface Ruthenium(II/III) Single Site for CO Activation

Liqun Kang; Bolun Wang; Adam Thetford; Ke Wu; Mohsen Danaie; Qian He; Emma K Gibson; Ling-Dong Sun; Hiroyuki Asakura; C Richard A Catlow; Feng Ryan Wang

doi:10.1002/anie.202008370

Design, Identification, and Evolution of a Surface Ruthenium(II/III) Single Site for CO Activation

Angew Chem Int Ed Engl. 2021 Jan 18;60(3):1212-1219. doi: 10.1002/anie.202008370. Epub 2020 Nov 13.

Authors

Liqun Kang¹, Bolun Wang¹, Adam Thetford², Ke Wu³, Mohsen Danaie⁴, Qian He⁵, Emma K Gibson⁶, Ling-Dong Sun³, Hiroyuki Asakura⁷, C Richard A Catlow^{8

9}, Feng Ryan Wang¹

Affiliations

¹ Department of Chemical Engineering, University College London, London, WC1E 7JE, UK.
² Department of Chemistry, The University of Manchester, Manchester, M13 9PL, UK.
³ College of Chemistry and Molecular Engineering, Peking University, Beijing, 100871, China.
⁴ Electron Physical Science Imaging Centre, Diamond Light Source, Didcot, OX11 0DE, UK.
⁵ Department of Materials Science and Engineering, National University of Singapore, Singapore, 117575, Singapore.
⁶ School of Chemistry, University of Glasgow, Glasgow, G12 8QQ, UK.
⁷ Elements Strategy Initiative for Catalysts & Batteries, Kyoto University, Kyoto, 615-8245, Japan.
⁸ Department of Chemistry, University College London, London, WC1H 0AJ, UK.
⁹ School of Chemistry, Cardiff University, Cardiff, CF10 3AT, UK.

Abstract

Ru^II compounds are widely used in catalysis, photocatalysis, and medical applications. They are usually obtained in a reductive environment as molecular O₂ can oxidize Ru^II to Ru^III and Ru^IV . Here we report the design, identification and evolution of an air-stable surface [bipy-Ru^II (CO)₂ Cl₂ ] site that is covalently mounted onto a polyphenylene framework. Such a Ru^II site was obtained by reduction of [bipy-Ru^III Cl₄ ]^- with simultaneous ligand exchange from Cl^- to CO. This structural evolution was witnessed by a combination of in situ X-ray and infrared spectroscopy studies. The [bipy-Ru^II (CO)₂ Cl₂ ] site enables oxidation of CO with a turnover frequency of 0.73×10^-2 s^-1 at 462 K, while the Ru^III site is completely inert. This work contributes to the study of structure-activity relationship by demonstrating a practical control over both geometric and electronic structures of single-site catalysts at molecular level.

Keywords: X-ray absorption spectroscopy; heterogeneous catalysis; ruthenium(II/III) complexes; single site; surface coordination chemistry.

Publication types

Research Support, Non-U.S. Gov't