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Daniel G. Nocera. Esswein, Arthur J Massachusetts Institute of Technology. Dept. of Chemistry. Massachusetts Institute of Technology. Department of Chemistry 2008-03-27T18:32:09Z 2008-03-27T18:32:09Z 2007 2007 http://hdl.handle.net/1721.1/40970 213296179 Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Chemistry, 2007. Vita. Includes bibliographical references. Broadly defined this thesis has focused on the design and study of molecular catalysts that engender multi-electron reactions and photoreactions on small molecule substrates relevant to solar energy conversion. Specifically the molecular design elements employed have focused on bimetallic complexes of late transition metals that exhibit an unusual two-electron mixed valence ground state. Initial studies focused on the mechanistic elucidation of the reported photocatalytic production of hydrogen from homogeneous hydrohalic acid solution using a two-electron mixed valence dirhodium complex. Studies aimed at understanding and improving the photochemical quantum efficiency for challenging M-X (X = CI, Br-) bond photoactivations were undertaken by incorporating gold into a heterobimetallic rhodium-gold construct. Additionally the organometallic reactivity of two-electron mixed valence diiridium cores was explored with a specific emphasis on C-H bond activations in order to extend the cooperative bimetallic reactivity observed in the dirhodium systems beyond HX and H2 substrates to alkanes and arenes. by Arthur J. Esswein. Ph.D. 183 p. eng Massachusetts Institute of Technology M.I.T. theses are protected by copyright. They may be viewed from this source for any purpose, but reproduction or distribution in any format is prohibited without written permission. See provided URL for inquiries about permission. http://dspace.mit.edu/handle/1721.1/7582 Chemistry. Late transition metal bimetallics for photocatalytic hydrogen production, M-X and C-H bond activation Thesis application/pdf Publication unknown unknown <Publication xmlns="https://www.openaire.eu/cerif-profile/1.1/" id="6be970e9-e49a-400e-a453-2dcebda926ff"> <Type xmlns="https://www.openaire.eu/cerif-profile/vocab/COAR_Publication_Types">http://purl.org/coar/resource_type/c_1843</Type> <Language>eng</Language> <Title>Late transition metal bimetallics for photocatalytic hydrogen production, M-X and C-H bond activation</Title> <PublishedIn> <Publication> </Publication> </PublishedIn> <PublicationDate>2007</PublicationDate> <Authors> <Author> <DisplayName>Esswein, Arthur J</DisplayName> <Affiliation> <OrgUnit> </OrgUnit> </Affiliation> </Author> </Authors> <Editors> </Editors> <Publishers> <Publisher> <DisplayName>Massachusetts Institute of Technology</DisplayName> <OrgUnit /> </Publisher> </Publishers> <License>http://dspace.mit.edu/handle/1721.1/7582</License> <Keyword>Chemistry.</Keyword> <Abstract>Broadly defined this thesis has focused on the design and study of molecular catalysts that engender multi-electron reactions and photoreactions on small molecule substrates relevant to solar energy conversion. Specifically the molecular design elements employed have focused on bimetallic complexes of late transition metals that exhibit an unusual two-electron mixed valence ground state. Initial studies focused on the mechanistic elucidation of the reported photocatalytic production of hydrogen from homogeneous hydrohalic acid solution using a two-electron mixed valence dirhodium complex. Studies aimed at understanding and improving the photochemical quantum efficiency for challenging M-X (X = CI, Br-) bond photoactivations were undertaken by incorporating gold into a heterobimetallic rhodium-gold construct. Additionally the organometallic reactivity of two-electron mixed valence diiridium cores was explored with a specific emphasis on C-H bond activations in order to extend the cooperative bimetallic reactivity observed in the dirhodium systems beyond HX and H2 substrates to alkanes and arenes.</Abstract> <Access xmlns="http://purl.org/coar/access_right" > </Access> </Publication>