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This content will become publicly available on February 27, 2019

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

For this research, well-defined organoplatinum(IV) sites were grafted on a Zn(II)-modified SiO 2 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/SiO 2, 1). In addition, computational modeling suggests that the surface reaction of (MeCp)PtMe 3 with Zn(II)-modified SiO 2 support is thermodynamically favorable (ΔG = -12.4 kcal/mol), likely due to the increased acidity of the hydroxyl group, as indicated by NH 3-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.
Authors:
ORCiD logo [1] ;  [1] ;  [1] ;  [1] ; ORCiD logo [1] ;  [2] ;  [3] ; ORCiD logo [4] ;  [5] ; ORCiD logo [1]
  1. Argonne National Lab. (ANL), Lemont, IL (United States). Chemical Sciences and Engineering Division
  2. Argonne National Lab. (ANL), Lemont, IL (United States). Energy Sciences Division
  3. Ames Lab., Ames, IA (United States)
  4. Ames Lab., Ames, IA (United States); Iowa State Univ., Ames, IA (United States). Department of Chemistry
  5. Argonne National Lab. (ANL), Lemont, IL (United States). Chemical Sciences and Engineering Division ; Northwestern Univ., Evanston, IL (United States). Department of Chemistry
Publication Date:
Report Number(s):
IS-J-9598
Journal ID: ISSN 0002-7863
Grant/Contract Number:
AC02-06CH11357; AC02-07CH11358
Type:
Accepted Manuscript
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 140; Journal Issue: 11; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society (ACS)
Research Org:
Ames Laboratory (AMES), Ames, IA (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
OSTI Identifier:
1427735