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Evidence for Redox Mechanisms in Organometallic Chemisorption and Reactivity on Sulfated Metal Oxides

TitleEvidence for Redox Mechanisms in Organometallic Chemisorption and Reactivity on Sulfated Metal Oxides
Publication TypeJournal Article
Year of Publication2018
AuthorsKlet, RC, Kaphan, DM, Liu, C, Yang, C, Kropft, AJ, Perras, FA, Pruski, M, Hock, AS, Delferro, M
JournalJournal of the American Chemical Society
Volume140
Pagination6308-6316
Date Published05
Type of ArticleArticle
ISBN Number0002-7863
Accession NumberWOS:000433404000021
Keywords100-percent active-sites, arene, chemistry, dynamic nuclear-polarization, enhanced, h bond activation, hydrogenation, n-butane isomerization, nmr-spectroscopy, polymerization catalysts, site heterogeneous catalysts, solid acid catalysts, state p-31 nmr
Abstract

nometallic precursors toward trityl cation ([Ph3C](+)), a Lewis acid known to effect formal hydride abstraction by one-electron oxidation followed by hydrogen abstraction. Organometallic deuterium incorporation was found to be correlated with surface sulfate concentration as well as the extent of dehydration under thermal activation conditions of SA and SZ supports. Surface sulfate concentration dependence, in conjunction with a computational study of surface electron affinity, indicates an electron-deficient pyrosulfate species as the redox-active moiety. These results provide further evidence for the ability of sulfated metal oxides to participate in redox chemistry not only toward organometallic complexes but also in the larger context of their application as catalysts for the transformation of light alkanes.

DOI10.1021/jacs.8b00995
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3D Catalysis