Publication Date

5-11-2018

Department

Ames Laboratory; Chemistry

Campus Units

Chemistry, Ames Laboratory

Report Number

IS-J 9599

DOI

10.1021/acscatal.8b00855

Journal Title

ACS Catalysis

Volume Number

8

Issue Number

6

First Page

5363

Last Page

5373

Abstract

Systematic study of the interactions between organometallic catalysts and metal oxide support materials is essential for the realization of rational design in heterogeneous catalysis. Herein we describe the stoichiometric and cata-lytic chemistry of a [Cp*(PMe3)Ir(III)] complex chemisorbed on a variety of acidic metal oxides as a multifaceted probe for stereoelectronic communication between the support and organometallic center. Electrophilic bond activation was explored in the context of stoichiometric hydrogenolysis as well as catalytic H/D exchange. Further information was ob-tained from the observation of processes related to dynamic exchange between grafted organometallic species and those in solution. The supported organometallic species were characterized by a variety of spectroscopic techniques including dynamic nuclear polarization-enhanced solid-state NMR spectroscopy, diffuse reflectance infrared Fourier transform spectroscopy, and X-ray absorption spectroscopy. Strongly acidic modified metal oxides such as sulfated zirconia engen-der high levels of activity toward electrophilic bond activation of both sp2 and sp3 C–H bonds, including the rapid deuter-ation of methane at room temperature; however, the global trend for the supports studied here does not suggest a direct correlation between activity and surface Brønsted acidity.

Language

en

Department of Energy Subject Categories

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Publisher

Iowa State University Digital Repository, Ames IA (United States)

Available for download on Saturday, May 11, 2019

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