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

Research output: Contribution to journalArticle

8 Citations (Scopus)

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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Hydrogenation
Silicon Dioxide
Aniline Compounds
Silica
Nitriles
Catalysts
Halogens
Toluene
Alkenes
Hydroxyl Radical
Polarization
Spectrum Analysis
Hydrogenolysis
Nitrobenzene
Surface reactions
Organometallics
Temperature programmed desorption
Aniline
Butadiene
Butenes

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., ... 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

Chemoselective Hydrogenation with Supported Organoplatinum(IV) Catalyst on Zn(II)-Modified Silica. / Camacho-Bunquin, Jeffrey; Ferrandon, Magali; Sohn, Hyuntae; Yang, Dali; Liu, Cong; Ignacio-De Leon, Patricia Anne; Perras, Frédéric A.; Pruski, Marek; Stair, Peter C; Delferro, Massimiliano.

In: Journal of the American Chemical Society, Vol. 140, No. 11, 21.03.2018, p. 3940-3951.

Research output: Contribution to journalArticle

Camacho-Bunquin, J, Ferrandon, M, Sohn, H, Yang, D, Liu, C, Ignacio-De Leon, PA, Perras, FA, Pruski, M, Stair, PC & Delferro, M 2018, 'Chemoselective Hydrogenation with Supported Organoplatinum(IV) Catalyst on Zn(II)-Modified Silica', Journal of the American Chemical Society, vol. 140, no. 11, pp. 3940-3951. https://doi.org/10.1021/jacs.7b11981
Camacho-Bunquin J, Ferrandon M, Sohn H, Yang D, Liu C, Ignacio-De Leon PA et al. Chemoselective Hydrogenation with Supported Organoplatinum(IV) Catalyst on Zn(II)-Modified Silica. Journal of the American Chemical Society. 2018 Mar 21;140(11):3940-3951. https://doi.org/10.1021/jacs.7b11981
Camacho-Bunquin, Jeffrey ; Ferrandon, Magali ; Sohn, Hyuntae ; Yang, Dali ; Liu, Cong ; Ignacio-De Leon, Patricia Anne ; Perras, Frédéric A. ; Pruski, Marek ; Stair, Peter C ; Delferro, Massimiliano. / Chemoselective Hydrogenation with Supported Organoplatinum(IV) Catalyst on Zn(II)-Modified Silica. In: Journal of the American Chemical Society. 2018 ; Vol. 140, No. 11. pp. 3940-3951.
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