Stabilizing unstable species through single-site isolation: A catalytically active Ta-V trialkyl in a porous organic polymer

TitleStabilizing unstable species through single-site isolation: A catalytically active Ta-V trialkyl in a porous organic polymer
Publication TypeJournal Article
Year of Publication2013
AuthorsTanabe KK, Siladke NA, Broderick EM, Kobayashi T, Goldston JF, Weston MH, Farha OK, Hupp JT, Pruski M, Mader EA, Johnson MJA, Nguyen ST
Journal TitleChemical Science
Volume4
Pages2483-2489
Date Published04/01
Type of ArticleArticle
ISBN Number2041-6520
Accession NumberWOS:000318559700024
Keywordsaromatic framework, catalysis, complexes, gas, high-surface-area, hydrogen storage, inorganic, metathesis, networks, oxides, tantalum
Abstract

A catechol-functionalized porous organic polymer (POP) has been successfully metallated with a Ta-V trialkyl and remains thermally and structurally robust. The resulting POP-supported (catecholato)Ta-V trialkyl sites remain accessible to small molecules and can undergo reactions to yield stable, monomeric complexes that are quite different from those observed with the homogeneous analogues. Using a combination of reactivity studies, high-resolution solid-state NMR spectroscopy, and X-ray absorption spectroscopy (XAS), we are able to precisely determine the functionality and coordination environment of the active (catecholato)Ta-V trialkyl site and its products in reactions with Bronsted acids. Additionally, the Ta-metallated POP was found to have enhanced catalytic activity in the hydrogenation of cyclohexene and toluene relative to a homogeneous analogue.

URL<Go to ISI>://WOS:000318559700024
DOI10.1039/c3sc22268c