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Title: Determination of the dominant catalyst derived from the classic [RhCp*Cl₂]₂ precatalyst system: Is it single-metal Rh₁Cp*-based, subnanometer Rh₄ cluster-based, or Rh(0)n nanoparticle-based cyclohexene hydrogenation catalysis at room temperature and mild pressures?

Determining the kinetically dominant catalyst in a given catalytic system is a forefront topic in catalysis. The [RhCp*Cl₂]₂ (Cp* =[η⁵-C₅(CH₃)₅]) system pioneered by Maitlis and co-workers is a classic precatalyst system from which homogeneous mononuclear Rh₁, subnanometer Rh₄ cluster, and heterogeneous polymetallic Rh(0)n nanoparticle have all arisen as viable candidates for the true hydrogenation catalyst, depending on the precise substrate, H₂ pressure, temperature, and catalyst concentration conditions. Addressed herein is the question of whether the prior assignment of homogeneous, mononuclear Rh₁Cp*-based catalysis is correct, or are trace Rh₄ subnanometer clusters or possibly Rh(0)n nanoparticles the dominant, actual cyclohexene hydrogenation catalyst at 22 °C and 2.7 atm initial H₂ pressure? The observation herein of Rh₄ species by in operando-X-ray absorption fine structure (XAFS) spectroscopy, at the only slightly more vigorous conditions of 26 °C and 8.3 atm H₂ pressure, and the confirmation of Rh₄ clusters by ex situ mass spectroscopy raises the question of the dominant, room temperature, and mild pressure cyclohexene hydrogenation catalyst derived from the classic [RhCp*Cl₂]₂ precatalyst pioneered by Maitlis and co-workers. Ten lines of evidence are provided herein to address the nature of the true room temperature and mild pressure cyclohexene hydrogenation catalyst derived from [RhCp*Cl₂]₂.more » Especially significant among those experiments are quantitative catalyst poisoning experiments, in the present case using 1,10-phenanthroline. Those poisoning studies allow one to distinguish mononuclear Rh₁, subnanometer Rh₄ cluster, and Rh(0)n nanoparticle catalysis hypotheses. The evidence obtained provides a compelling case for a mononuclear, Rh₁Cp*-based cyclohexene hydrogenation catalyst at 22 °C and 2.7 atm H₂ pressure. The resultant methodology, especially the quantitative catalyst poisoning experiments in combination with in operando spectroscopy, is expected to be more broadly applicable to the study of other systems and the “what is the true catalyst?” question. The authors would like to thank Finke Group members and Prof. Saim Ö zkar for their valuable input as this work was proceeding. This work was supported at Colorado State University by the U.S. Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences, vial DOE Grant SE-FG402-03ER15453. The work at PNNL was also supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geo-sciences & Biosciences. Pacific Northwest National Laboratory (PNNL) is a multiprogram national laboratory operated for the DOE by Battelle. XSD/PNC facilities at the Advanced Photon Source and research at these facilities are supported by the U.S. Department of Energy, Basic Energy Sciences; a Major Resources Support Grant from NSERC; the University of Washington; the Canadian Light Source; and the Advanced Photon Source. Use of the Advanced Photon Source, an Office of Science User Facility operated for the U.S. Department of Energy Office of Science by Argonne National Laboratory was supported by the U.S. DOE under Contract No. DE-AC02- 06CH11357.« less
Authors:
 [1] ;  [2] ;  [2] ;  [3] ;  [1]
  1. Colorado State Univ., Fort Collins, CO (United States)
  2. Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
  3. Univ. of Michigan, Ann Arbor, MI (United States)
Publication Date:
OSTI Identifier:
1212230
Report Number(s):
PNNL-SA--111895
Journal ID: ISSN 2155-5435; KC0302010
DOE Contract Number:
AC05-76RL01830
Resource Type:
Journal Article
Resource Relation:
Journal Name: ACS Catalysis; Journal Volume: 5; Journal Issue: 6
Publisher:
American Chemical Society
Research Org:
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
Sponsoring Org:
USDOE
Country of Publication:
United States
Language:
English
Subject:
catalysis; determination of the dominant catalyst; catalyst poisoning studies; rhodium; organometallic complex catalysis; subnanometer cluster catalysis; nanoparticle catalysis; XAFS; in operando spectroscopic studies