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

Jeffrey Camacho-Bunquin, Magali Ferrandon, Hyuntae Sohn, Dali Yang, Cong Liu, Patricia Anne Ignacio-De Leon, Frédéric A. Perras, Marek Pruski, Peter C Stair, Massimiliano Delferro

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Abstract

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-H2 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 (ΔG = -12.4 kcal/mol), likely due to the increased acidity of the hydroxyl group, as indicated by NH3-TPD and DNP-enhanced 17O{1H} 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.

Original languageEnglish
Pages (from-to)3940-3951
Number of pages12
JournalJournal of the American Chemical Society
Volume140
Issue number11
DOIs
Publication statusPublished - Mar 21 2018

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ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Camacho-Bunquin, J., Ferrandon, M., Sohn, H., Yang, D., Liu, C., Ignacio-De Leon, P. A., Perras, F. A., Pruski, M., Stair, P. C., & Delferro, M. (2018). Chemoselective Hydrogenation with Supported Organoplatinum(IV) Catalyst on Zn(II)-Modified Silica. Journal of the American Chemical Society, 140(11), 3940-3951. https://doi.org/10.1021/jacs.7b11981