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Design, identification and evolution of surface ruthenium (II/III) single‐site for CO activation
Authors:
Liqun
Kang
(University College London)
,
Bolun
Wang
(University College London)
,
Adam
Thetford
(The University of Manchester)
,
Ke
Wu
(Peking University)
,
Mohsen
Danaie
(Diamond Light Source)
,
Qian
He
(National University of Singapore)
,
Emma
Gibson
(University of Glasgow)
,
Ling-dong
Sun
(Peking University)
,
Hiroyuki
Asakura
(Kyoto University)
,
Richard
Catlow
(Cardiff University)
,
Feng Ryan
Wang
(University College London)
Co-authored by industrial partner:
No
Type:
Journal Paper
Journal:
Angewandte Chemie International Edition
State:
Published (Approved)
Published:
September 2020
Diamond Proposal Number(s):
16966
,
17559
,
18909
,
19246
,
19318
,
20643
,
20847
,
17377
,
15151
,
14239

Abstract: Ru(II) compounds are widely used in catalysis, photocatalysis and medical applications. They are usually obtained in reductive environment as molecular O 2 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 Cl 2 ] site that is covalently mounted onto a polyphenylene framework. Such Ru(II) site was obtained by reduction of ‐[bipy‐Ru(III)Cl 4 ] ‐ 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 Cl 2 ] 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 studies of structure‐activity relationship by demonstrating a practical control over both geometric and electronic structures of single‐site catalysts at molecular level, which can be further applied in other single site catalyst researches.
Journal Keywords: heterogeneous catalysis; Ruthenium (II) complex; Surface coordination chemistry; Single-site; X-ray Absorption Spectroscopy
Subject Areas:
Chemistry
Diamond Offline Facilities:
Electron Physical Sciences Imaging Centre (ePSIC)
Instruments:
B18-Core EXAFS
,
E01-JEM ARM 200CF
,
E02-JEM ARM 300CF
Other Facilities: BL6N1 beamline at Aichi Synchrotron Radiation Center; ISISS beamline at BESSY II
Documents:
anie.202008370.pdf