Catalytic proton reduction with transition metal complexes of the redox-active ligand bpy2PYMe

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dc.contributor.author Nippe, Micheal
dc.contributor.author Khnayzer, Rony S.
dc.contributor.author Panetier, Julien A.
dc.contributor.author Zee, David Z.
dc.contributor.author Olaiya, Babatunde S.
dc.contributor.author Head-Gordon, Martin
dc.contributor.author Chang, Christopher J.
dc.contributor.author Castellano, Felix N.
dc.contributor.author Long, Jeffrey R.
dc.date.accessioned 2017-11-03T07:03:48Z
dc.date.available 2017-11-03T07:03:48Z
dc.date.copyright 2013 en_US
dc.date.issued 2017-11-03
dc.identifier.issn 2041-6539 en_US
dc.identifier.uri http://hdl.handle.net/10725/6488
dc.description.abstract A new pentadentate, redox-active ligand bpy2PYMe has been synthesized and its corresponding transition metal complexes of Fe2+ (1), Co2+ (2), Ni2+ (3), Cu2+ (4), and Zn2+ (5) have been investigated for electro- and photo-catalytic proton reduction in acetonitrile and water, respectively. Under weak acid conditions, the Co complex displays catalytic onset at potentials similar to those of the ligand centered reductions in the absence of acid. Related Co complexes devoid of ligand redox activity catalyze H2 evolution under similar conditions at significantly higher overpotentials, showcasing the beneficial effect of combining ligand-centered redox activity with a redox-active Co center. Furthermore, turnover numbers as high as 1630 could be obtained under aqueous photocatalytic conditions using [Ru(bpy)3]2+ as a photosensitizer. Under those conditions catalytic hydrogen production was solely limited by photosensitizer stability. Introduction of an electron withdrawing CF3 group into the pyridine moiety of the ligand as in bpy2PYMe-CF3 renders its corresponding Co complex 6 less active for proton reduction in electro- and photocatalytic experiments. This surprising effect of ligand substitution was investigated by means of density functional theory calculations which suggest the importance of electronic communication between Co1+ and the redox-active ligand. Taken together, the results provide a path forward in the design of robust molecular catalysts in aqueous media with minimized overpotential by exploiting the synergy between redox-active metal and ligand components. en_US
dc.language.iso en en_US
dc.title Catalytic proton reduction with transition metal complexes of the redox-active ligand bpy2PYMe en_US
dc.type Article en_US
dc.description.version Published en_US
dc.author.school SAS en_US
dc.author.idnumber 200501196 en_US
dc.author.department Natural Sciences en_US
dc.description.embargo N/A en_US
dc.relation.journal Chemical Science en_US
dc.journal.volume 4 en_US
dc.article.pages 3934-3945 en_US
dc.identifier.doi http://dx.doi.org/ 10.1039/c3sc51660a en_US
dc.identifier.ctation Nippe, M., Khnayzer, R. S., Panetier, J. A., Zee, D. Z., Olaiya, B. S., Head-Gordon, M., ... & Long, J. R. (2013). Catalytic proton reduction with transition metal complexes of the redox-active ligand bpy2PYMe. Chemical Science, 4(10), 3934-3945. en_US
dc.author.email rony.khnayzer@lau.edu.lb en_US
dc.identifier.tou http://libraries.lau.edu.lb/research/laur/terms-of-use/articles.php en_US
dc.identifier.url http://pubs.rsc.org/is/content/articlehtml/2013/sc/c3sc51660a en_US
dc.orcid.id https://orcid.org/0000-0001-7775-0027 en_US
dc.author.affiliation Lebanese American University en_US

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