Evidence for Redox Mechanisms in Organometallic Chemisorption and Reactivity on Sulfated Metal Oxides

Klet, Rachel C.; Kaphan, David M.; Liu, Cong; Yang, Ce; Kropf, A. Jeremy; Perras, Frederic A.; Pruski, Marek; Hock, Adam S.; Delferro, Massimiliano

doi:10.1021/jacs.8b00995

Title: Evidence for Redox Mechanisms in Organometallic Chemisorption and Reactivity on Sulfated Metal Oxides

Journal Article · Mon Apr 09 00:00:00 EDT 2018 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.8b00995· OSTI ID:1435752

^[1]; Kaphan, David M. ^[1];

^[1]; Yang, Ce ^[1]; Kropf, A. Jeremy ^[1]; Perras, Frederic A. ^[2];

^[3];

^[4];

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Argonne National Lab. (ANL), Lemont, IL (United States)
Ames Lab., Ames, IA (United States)
Ames Lab. and Iowa State Univ., Ames, IA (United States)
Argonne National Lab. (ANL), Lemont, IL (United States); Illinois Institute of Technology, Chicago, IL (United States)

The chemical and electronic interaction of organometallic species with metal oxide support materials is of fundamental importance for the development of new classes of catalytic materials. Chemisorption of Cp*(PMe3)IrMe2 on sulfated alu-mina (SA) and sulfated zirconia (SZ) led to an unexpected redox mechanism for deuteration of the ancillary Cp* ligand. Evidence for this oxidative mechanism was provided by studying the analogous homogeneous reactivity of the organome-tallic precursors toward trityl cation ([Ph3C]+), a Lewis acid known to effect formal hydride abstraction by one electron oxidation followed by hydrogen abstraction. Organometallic deuterium incorporation was found to be correlated with surface sulfate concentration, as well as the extent of dehydration under thermal activation conditions of sulfated alumi-na and sulfated zirconia supports. Surface sulfate concentration dependence, in conjunction with a computational study of surface electron affinity, indicates an electron deficient pyrosulfate species as the redox active moiety. These results provide further evidence for the ability of sulfated metal oxides to participate in redox chemistry not only toward organ-ometallic complexes, but also in the larger context of their application as catalysts for the transformation of light alkanes.

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Research Organization:: Ames Lab., Ames, IA (United States); Argonne National Lab. (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-06CH11357; AC02-07CH11358

OSTI ID:: 1435752

Alternate ID(s):: OSTI ID: 1460729

Report Number(s):: IS-J-9600

Journal Information:: Journal of the American Chemical Society, Vol. 140, Issue 20; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 24 works

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