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

Journal of the American Chemical Society
J Camacho-BunquinM Delferro

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 (Δ G = -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.

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Citations

Feb 19, 2019·Chemistry : a European Journal·Martin BrodrechtGerd Buntkowsky
Feb 3, 2020·The Journal of Chemical Physics·Nathaniel E RicheyStacey F Bent
Aug 30, 2019·Physical Chemistry Chemical Physics : PCCP·Frédéric A PerrasMarek Pruski
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May 9, 2021·Journal of Magnetic Resonance·Amrit VenkateshAaron J Rossini
May 22, 2021·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·Takeshi Kobayashi, Marek Pruski
Jul 1, 2021·Chemistry : a European Journal·Yusuke IshizakaJun-Chul Choi
Aug 28, 2018·Journal of the American Chemical Society·Keith SearlesChristophe Copéret
Nov 21, 2018·Journal of the American Chemical Society·Mengqi ShenShouheng Sun
Oct 23, 2020·Journal of the American Chemical Society·Amrit VenkateshAaron J Rossini
Dec 29, 2021·Inorganic Chemistry·Frédéric A PerrasAaron D Sadow

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