skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Metal Nanoparticles Catalyzed Selective Carbon–Carbon Bond Activation in the Liquid Phase

Journal Article · · Journal of the American Chemical Society
DOI:https://doi.org/10.1021/jacs.6b03977· OSTI ID:1336474
 [1];  [2];  [2];  [2];  [2];  [2];  [2];  [1]
  1. Department of Chemistry, University of California, Berkeley, California 94720, United States; Chemical Science Division, Lawrence Berkeley National Laboratory, 1 Cyclotron Road, Berkeley, California 94720, United States
  2. Department of Chemistry, University of California, Berkeley, California 94720, United States
+ Show Author Affiliations

Understanding the C-C bond activation mechanism is essential for developing the selective production of hydrocarbons in the petroleum industry and for selective polymer decomposition. Here, ring-opening reactions of cyclopropane derivatives under hydrogen catalyzed by metal nanoparticles (NPs) in the liquid phase were studied. 40-atom rhodium (Rh) NPs, encapsulated by dendrimer molecules and supported in mesoporous silica, catalyzed the ring opening of cyclopropylbenzene at room temperature under hydrogen in benzene, and the turnover frequency (TOF) was higher than other metals or the Rh homogeneous catalyst counterparts. Comparison of reactants with various substitution groups showed that electron donation on the three-membered ring boosted the TOF of ring opening. The linear products formed with 100% selectivity for ring opening of all reactants catalyzed by the Rh NP. Surface Rh(0) acted as the active site in the NP. The capping agent played an important role in the ring-opening reaction kinetics. Larger particle size tended to show higher TOF and smaller reaction activation energy for Rh NPs encapsulated in either dendrimer or poly(vinylpyrrolidone). The generation/size of dendrimer and surface group also affected the reaction rate and activation energy.

Research Organization:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division
Grant/Contract Number:
AC02-05CH11231
OSTI ID:
1336474
Alternate ID(s):
OSTI ID: 1464139
Journal Information:
Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Vol. 138 Journal Issue: 27; ISSN 0002-7863
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 35 works
Citation information provided by
Web of Science

References (28)

Mechanistic Insight into Size-Dependent Activity and Durability in Pt/CNT Catalyzed Hydrolytic Dehydrogenation of Ammonia Borane journal November 2014
Catalytic Hydrogenolysis of Biphenylene with Platinum, Palladium, and Nickel Phosphine Complexes journal October 1998
Rhodium-Catalyzed Ring Opening of Benzocyclobutenols with Site-Selectivity Complementary to Thermal Ring Opening journal October 2012
Palladium-Catalyzed Diastereo- and Enantioselective Formal [3 + 2]-Cycloadditions of Substituted Vinylcyclopropanes journal October 2012
Dendrimer Templated Synthesis of One Nanometer Rh and Pt Particles Supported on Mesoporous Silica: Catalytic Activity for Ethylene and Pyrrole Hydrogenation journal July 2008
Molecular catalysis science: Perspective on unifying the fields of catalysis journal April 2016
Catalytic C–C Bond Activations via Oxidative Addition to Transition Metals journal June 2015
Dendrimer-Encapsulated Pt Nanoparticles: Synthesis, Characterization, and Applications to Catalysis journal March 1999
The Catalytic Hydrogenolysis of Small Carbon Rings. journal April 1963
Transition-Metal-Mediated Cleavage and Activation of C-C Single Bonds journal February 2012
Metal Insertion into C−C Bonds in Solution journal April 1999
The hydrogenolysis of cyclopropane on a platinum stepped single crystal at atmospheric pressure journal August 1974
Fe-Catalyzed Allylic C–C-Bond Activation: Vinylcyclopropanes As Versatile a1,a3,d5-Synthons in Traceless Allylic Substitutions and [3 + 2]-Cycloadditions journal March 2012
Copper‐Catalyzed Aerobic Oxidative CC Bond Cleavage for CN Bond Formation: From Ketones to Amides journal May 2014
Planar oxide supported rhodium nanoparticles as model catalysts journal October 2010
Control of selectivity in heterogeneous catalysis by tuning nanoparticle properties and reactor residence time journal September 2012
Effect of Pd Nanoparticle Size on the Catalytic Hydrogenation of Allyl Alcohol
  • Wilson, Orla M.; Knecht, Marc R.; Garcia-Martinez, Joaquin C.
  • Journal of the American Chemical Society, Vol. 128, Issue 14, p. 4510-4511 https://doi.org/10.1021/ja058217m
journal April 2006
Activation of a carbon–carbon bond in solution by transition-metal insertion journal August 1993
Rhodium(I)-Catalyzed Successive Double Cleavage of Carbon−Carbon Bonds of Strained Spiro Cyclobutanones journal October 1997
Directing Group Enhanced Carbonylative Ring Expansions of Amino-Substituted Cyclopropanes: Rhodium-Catalyzed Multicomponent Synthesis of N-Heterobicyclic Enones journal March 2013
Catalytic Cyclopropane Hydrogenation on Platinum(111) Using In Situ Soft X-ray Methods † journal April 2000
Transition metal-catalyzed carbon–carbon bond activation journal January 2004
Selective, Catalytic Carbon−Carbon Bond Activation and Functionalization Promoted by Late Transition Metal Catalysts journal January 2003
Formation of Nickeladihydropyran by Oxidative Addition of Cyclopropyl Ketone. Key Intermediate in Nickel-Catalyzed Cycloaddition journal April 2006
Structure Sensitivity of Alkynol Hydrogenation on Shape- and Size-Controlled Palladium Nanocrystals: Which Sites Are Most Active and Selective? journal August 2011
Petroleum Refining book March 2007
The kinetics and mechanism of the catalytic hydrogenation of cyclopropane journal January 1972
Converting homogeneous to heterogeneous in electrophilic catalysis using monodisperse metal nanoparticles journal November 2009

Similar Records

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
36 MATERIALS SCIENCE
77 NANOSCIENCE AND NANOTECHNOLOGY