TY - JOUR
T1 - Chemoselective Hydrogenation with Supported Organoplatinum(IV) Catalyst on Zn(II)-Modified Silica
AU - Camacho-Bunquin, Jeffrey
AU - Ferrandon, Magali
AU - Sohn, Hyuntae
AU - Yang, Dali
AU - Liu, Cong
AU - Ignacio-De Leon, Patricia Anne
AU - Perras, Frédéric A.
AU - Pruski, Marek
AU - Stair, Peter C.
AU - Delferro, Massimiliano
N1 - Funding Information:
This work was supported by the U.S. Department of Energy (DOE) Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences, under Contract DE-AC02-06CH11357 (Argonne National Laboratory) and DE-AC02-07CH11358 (Ames Laboratory). The calculations were performed using the computational resources provided by the Laboratory Computing Resource Center (LCRC) at Argonne and National Energy Research Scientific Computing (NERSC) Center. Use of the Advanced Photon Source is supported by the U.S. Department of Energy, Office of Science and Office of the Basic Energy Sciences, under Contract DE-AC-02-06CH11357.
Publisher Copyright:
© 2018 American Chemical Society.
PY - 2018/3/21
Y1 - 2018/3/21
N2 - 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.
AB - 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.
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U2 - 10.1021/jacs.7b11981
DO - 10.1021/jacs.7b11981
M3 - Article
C2 - 29485277
AN - SCOPUS:85044343209
VL - 140
SP - 3940
EP - 3951
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
SN - 0002-7863
IS - 11
ER -