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Title: Kinetics and DFT studies of photoredox carbon–carbon bond cleavage reactions by molecular vanadium catalysts under ambient conditions
Authors: Gazi, Sarifuddin
Đokić, Miloš
Moeljadi, Adhitya Mangala Putra
Ganguly, Rakesh
Hirao, Hajime
Soo, Han Sen
Keywords: Visible Light Photoredox Catalysis
Selective Carbon-carbon Bond Cleavage
Issue Date: 2017
Source: Gazi, S., Đokić, M., Moeljadi, A. M. P., Ganguly, R., Hirao, H., & Soo, H. S. (2017). Kinetics and DFT studies of photoredox carbon–carbon bond cleavage reactions by molecular vanadium catalysts under ambient conditions. ACS Catalysis, 7(7), 4682-4691. doi:10.1021/acscatal.7b01036
Series/Report no.: ACS Catalysis
Abstract: Visible light assisted photocatalytic organic reactions have recently received intense attention as a versatile approach to achieve selective chemical transformations, including C−C and several C−X (X = N, O, S) bond formations under mild reaction conditions. The light harvesters in previous reports predominantly comprise ruthenium or iridium photosensitizers. In contrast, selective, photocatalytic aliphatic C−C bond cleavage reactions are scarce. The present study focuses on rationally designing VV oxo complexes as molecular, photoredox catalysts toward the selective activation and cleavage of a C−C bond adjacent to the alcohol group in aliphatic alcoholic substrates. We have employed kinetics measurements and DFT calculations to develop a candidate for the catalytic C−C bond activation reaction that is up to 7 times faster than our original vanadium complex. We have also identified a substrate where the C−C bond cleaves at rates 2.5−17 times faster, depending on the catalyst used. In order to better understand the effects of ligand modification on the thermodynamics and catalysis, DFT calculations were employed to reveal the orbital energies, the electronic transitions during the C−C bond cleavage, and the activation barriers. Our combined kinetics and computational studies indicate that the incorporation of electron-withdrawing groups at select sites of the ligand is essential for the development of active and stable vanadium photocatalysts for our C−C bond cleavage reactions.
DOI: 10.1021/acscatal.7b01036
Schools: School of Physical and Mathematical Sciences 
Rights: © 2017 American Chemical Society (ACS). This is the author created version of a work that has been peer reviewed and accepted for publication by ACS Catalysis, American Chemical Society (ACS). It incorporates referee’s comments but changes resulting from the publishing process, such as copyediting, structural formatting, may not be reflected in this document. The published version is available at: [].
Fulltext Permission: open
Fulltext Availability: With Fulltext
Appears in Collections:SPMS Journal Articles

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