Publication Date
5-11-2018
Department
Ames Laboratory; Chemistry
Campus Units
Chemistry, Ames Laboratory
OSTI ID+
1440975
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 catalytic 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 obtained 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 engender high levels of activity toward electrophilic bond activation of both sp2 and sp3 C–H bonds, including the rapid deuteration 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.
DOE Contract Number(s)
AC02-07CH11358; AC02-06CH11357
Language
en
Department of Energy Subject Categories
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE
Publisher
Iowa State University Digital Repository, Ames IA (United States)
