期刊
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
卷 140, 期 11, 页码 3940-3951出版社
AMER CHEMICAL SOC
DOI: 10.1021/jacs.7b11981
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资金
- U.S. Department of Energy (DOE), Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences [DE-AC02-06CH11357, DE-AC02-07CH11358]
- U.S. Department of Energy, Office of Science, and Office of the Basic Energy Sciences [DE-AC-02-06CH11357]
- Department of Energy
- MRCAT member institutions
- Laboratory Directed Research and Development (LDRD) program at the Ames Laboratory
- NSERC
- Government of Canada
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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