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Photochemical reductive elimination of halogen from transition metal complexes

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dc.contributor.advisor Daniel G. Nocera. en_US
dc.contributor.author Cook, Timothy R. (Timothy Raymond), 1982- en_US
dc.contributor.other Massachusetts Institute of Technology. Dept. of Chemistry. en_US
dc.date.accessioned 2010-09-02T17:25:50Z
dc.date.available 2010-09-02T17:25:50Z
dc.date.copyright 2010 en_US
dc.date.issued 2010 en_US
dc.identifier.uri http://hdl.handle.net/1721.1/58295
dc.description Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Chemistry, 2010. en_US
dc.description Vita. Cataloged from PDF version of thesis. en_US
dc.description Includes bibliographical references. en_US
dc.description.abstract This thesis is focused on the synthesis and study of transition metal complexes that undergo halogen elimination when irradiated with UV and visible light. This chemistry is relevant for solar energy storage schemes in which simple substrates such as HX (X = Cl, Br, OH) can be split to H2 and X2 in thermodynamically uphill photocycles. The activation of strong M-X bonds is a key requirement for efficient photocatalysts and represents the most challenging step of HX splitting schemes. Studies have focused on the design and characterization of late-metal phosphine complexes with an emphasis on chemical oxidation with halogen to give stable, halide-rich metal centers, and the subsequent photochemistry of the resulting complexes. The primary goal of this work was to increase the photo-efficiency of M-X bond activation as (1) the low quantum yield of halogen elimination had been implicated as the governing step determining the efficiency of previously reported HX splitting catalysts and (2) mechanistic studies on the nature of halogen elimination using laser kinetic techniques require a substantial concentration of transient photointermediates for signal to be observed. These targets spurred the development of a number of late-metal homo- and heterobimetallic complexes which undergo highly efficient halogen elimination, as well as the first reports of authentic X2 reductive elimination from a transition metal center and direct observation of M-X bond activation using transient absorption spectroscopy. en_US
dc.description.statementofresponsibility by Timothy R. Cook. en_US
dc.format.extent 180 p. en_US
dc.language.iso eng en_US
dc.publisher Massachusetts Institute of Technology en_US
dc.rights 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. en_US
dc.rights.uri http://dspace.mit.edu/handle/1721.1/7582 en_US
dc.subject Chemistry. en_US
dc.title Photochemical reductive elimination of halogen from transition metal complexes en_US
dc.type Thesis en_US
dc.description.degree Ph.D. en_US
dc.contributor.department Massachusetts Institute of Technology. Dept. of Chemistry. en_US
dc.identifier.oclc 655269193 en_US


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