Journal
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 58, Issue 37, Pages 13140-13148Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.201907247
Keywords
enzyme catalysis; rhodium; ruthenium; spectro-electrochemistry; ultrafast spectroscopy
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Funding
- German Science Foundation [DI1517/11-1, CATALIGHT CRC/RR 234, 364549901]
- Thuringian State Government
- FCI (via a Chemiefonds-Stipendium)
- German Academic Exchange Service
- Konrad Adenauer foundation
- German Academic Scholarship Foundation
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Understanding photodriven multielectron reaction pathways requires the identification and spectroscopic characterization of intermediates and their excited-state dynamics, which is very challenging due to their short lifetimes. To the best of our knowledge, this manuscript reports for the first time on in situ spectroelectrochemistry as an alternative approach to study the excited-state properties of reactive intermediates of photocatalytic cycles. UV/Vis, resonance-Raman, and transient-absorption spectroscopy have been employed to characterize the catalytically competent intermediate [(tbbpy)(2)Ru-II(tpphz)(RhCp)-Cp-I*] of [(tbbpy)(2)Ru(tpphz)Rh(Cp*)Cl]Cl(PF6)(2) (Ru(tpphz)RhCp*), a photocatalyst for the hydrogenation of nicotinamide (NAD-analogue) and proton reduction, generated by electrochemical and chemical reduction. Electronic transitions shifting electron density from the activated catalytic center to the bridging tpphz ligand significantly reduce the catalytic activity upon visible-light irradiation.
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