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Chemoselective Hydrogenation with Supported Organoplatinum(IV) Catalyst on Zn(II)-Modified Silica

TitleChemoselective Hydrogenation with Supported Organoplatinum(IV) Catalyst on Zn(II)-Modified Silica
Publication TypeJournal Article
Year of Publication2018
AuthorsCamacho-Bunquin, J, Ferrandon, M, Sohn, H, Yang, DL, Liu, C, de Leon, PAIgnacio, Perras, FA, Pruski, M, Stair, PC, Delferro, M
JournalJournal of the American Chemical Society
Date Published03
Type of ArticleArticle
ISBN Number0002-7863
Accession NumberWOS:000428356000023
Keywordsarene hydrogenation, atomic, chemistry, co, dynamic nuclear-polarization, enhanced, layer deposition, nmr-spectroscopy, oxidation, selective hydrogenation, site heterogeneous catalysts, solid-state nmr, surface organometallic chemistry, water-gas shift

Well-defined organoplatinum(IV) sites were grafted on a Zn(II)-modified SiO2 support via surface organometallic chemistry in toluene at room temperature. Solid-state spectroscopies including XAS, DRIFTS, DRUV- vis, and solid-state (SS) NMR enhanced by dynamic nuclear polarization (DNP), as well as TPR-H-2 and TEM techniques revealed highly dispersed (methylcyclopentadienyl)methylplatinum(IV) sites on the surface ((MeCp)PtMe/Zn/SiO2, 1). In addition, computational modeling suggests that the surface reaction of (MeCp)PtMe3 with Zn(II)-modified SiO2 support is thermodynamically favorable (Delta G = -12.4 kcal/mol), likely due to the increased acidity of the hydroxyl group, as indicated by NH3-TPD and DNP-enhanced O-17{H-1} SSNMR. In situ DRIFTS and XAS hydrogenation experiments reveal the probable formation of a surface Pt(IV)-H upon hydrogenolysis of Pt-Me groups. The heterogenized organoplatinum(IV)-hydride sites catalyze the selective partial hydrogenation of 1,3-butadiene to butenes (up to 95%) and the reduction of nitrobenzene derivatives to anilines (up to 99%) with excellent tolerance of reduction-sensitive functional groups (olefin, carbonyl, nitrile, halogens) under mild reaction conditions.

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