Kang, L. et al. (2021) Design, identification, and evolution of a surface ruthenium(II/III) single site for CO activation. Angewandte Chemie (International Edition), 60(3), pp. 1212-1219. (doi: 10.1002/anie.202008370) (PMID:32978789) (PMCID:PMC7839529)
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Abstract
RuII compounds are widely used in catalysis, photocatalysis, and medical applications. They are usually obtained in a reductive environment as molecular O2 can oxidize RuII to RuIII and RuIV. Here we report the design, identification and evolution of an air-stable surface [bipy-RuII(CO)2Cl2] site that is covalently mounted onto a polyphenylene framework. Such a RuII site was obtained by reduction of [bipy-RuIIICl4]− 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-RuII(CO)2Cl2] site enables oxidation of CO with a turnover frequency of 0.73×10−2 s−1 at 462 K, while the RuIII 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.
| Item Type: | Articles |
|---|---|
| Additional Information: | The project is funded by EPSRC (EP/P02467X/1 and EP/S018204/2), Royal Society (RG160661, IES\R3\170097, IES\R1\191035, IES\R3\193038) and the Newton International Fellowship (NF170761). We acknowledge electron Physical Science Imaging Centre at Diamond Light Source (UK) for the STEM experiment (Proposal No. EM16966, EM17559, EM18909, EM19246, EM19318, EM20643, and EM20847). We acknowledge the B18 beamline of Diamond Light Source for XAFS experiment (Proposal No. SP17377). We thank the Diamond Light Source for the award of beamtime at B18 beamline as part of the UK Catalysis Hub Block Allocation Group (Proposal No. SP15151) and Energy Materials Block Allocation Group (Proposal No. SP14239). We acknowledge the BL6N1 beamline of Aichi Synchrotron Radiation Center (Japan) for the Ru L-edge and Cl K-edge XAFS measurements (Proposal No. 20190464). We acknowledge Helmholz-Zentrum Berlin for the beamtime at ISISS beamline in BESSY II (Proposal No. 191-08389 ST). We thank the UK Catalysis Hub for resources and support provided via membership of the UK Catalysis Hub Consortium and funding by EPSRC (grants EP/ K014706/2, EP/K014668/1, EP/K014854/1, EP/K014714/1 and EP/M013219/1). |
| Status: | Published |
| Refereed: | Yes |
| Glasgow Author(s) Enlighten ID: | Gibson, Dr Emma |
| Authors: | Kang, L., Wang, B., Thetford, A., Wu, K., Danaie, M., He, Q., Gibson, E. K., Sun, L.‐D., Asakura, H., Catlow, C. R. A., and Wang, F. R. |
| College/School: | College of Science and Engineering > School of Chemistry |
| Journal Name: | Angewandte Chemie (International Edition) |
| Publisher: | Wiley |
| ISSN: | 1433-7851 |
| ISSN (Online): | 1521-3773 |
| Published Online: | 25 September 2020 |
| Copyright Holders: | Copyright © 2021 The Authors |
| First Published: | First published in Angewandte Chemie (International Edition) 60(3): 1212-1219 |
| Publisher Policy: | Reproduced under a Creative Commons License |
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