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Title: Mechanistic Aspects of a Surface Organovanadium(III) Catalyst for Hydrocarbon Hydrogenation and Dehydrogenation

Abstract

Understanding the mechanisms of action for base metal catalysis of transformations typically associated with precious metals is essential for the design of technologies for a sustainable energy economy. Isolated transition-metal and post-transition-metal catalysts on oxides such as silica are generally proposed to effect hydrogenation and dehydrogenation by a mechanism featuring either σ-bond metathesis or heterolytic bond cleavage as the key bond activation step. In this work, an organovanadium(III) complex on silica, which is a precatalyst for both olefin hydrogenation and alkane dehydrogenation, is interrogated by a series of reaction kinetics and isotopic labeling studies in order to shed light on the operant mechanism for hydrogenation. The kinetic dependencies of the reaction components are potentially consistent with both the σ-bond metathesis and the heterolytic bond activation mechanisms; however, a key deuterium incorporation experiment definitively excludes the simple σ-bond metathesis mechanism. Alternatively, a two-electron redox cycle, rarely invoked for homologous catalyst systems, is also consistent with experimental observations. Evidence supporting the formation of a persistent vanadium(III) hydride upon hydrogen treatment of the as-prepared material is also presented.

Authors:
ORCiD logo [1];  [1]; ORCiD logo [1]; ORCiD logo [1];  [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]
  1. Argonne National Lab. (ANL), Argonne, IL (United States). Chemical Sciences and Engineering Division
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1576520
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
ACS Catalysis
Additional Journal Information:
Journal Volume: 9; Journal Issue: 12; Journal ID: ISSN 2155-5435
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; heterogeneous catalysis; hydrogenation; mechanistic study; organovanadium; supported organometallic catalysis

Citation Formats

Kaphan, David M., Ferrandon, Magali S., Langeslay, Ryan R., Celik, Gokhan, Wegener, Evan C., Liu, Cong, Niklas, Jens, Poluektov, Oleg G., and Delferro, Massimiliano. Mechanistic Aspects of a Surface Organovanadium(III) Catalyst for Hydrocarbon Hydrogenation and Dehydrogenation. United States: N. p., 2019. Web. doi:10.1021/acscatal.9b02800.
Kaphan, David M., Ferrandon, Magali S., Langeslay, Ryan R., Celik, Gokhan, Wegener, Evan C., Liu, Cong, Niklas, Jens, Poluektov, Oleg G., & Delferro, Massimiliano. Mechanistic Aspects of a Surface Organovanadium(III) Catalyst for Hydrocarbon Hydrogenation and Dehydrogenation. United States. doi:10.1021/acscatal.9b02800.
Kaphan, David M., Ferrandon, Magali S., Langeslay, Ryan R., Celik, Gokhan, Wegener, Evan C., Liu, Cong, Niklas, Jens, Poluektov, Oleg G., and Delferro, Massimiliano. Mon . "Mechanistic Aspects of a Surface Organovanadium(III) Catalyst for Hydrocarbon Hydrogenation and Dehydrogenation". United States. doi:10.1021/acscatal.9b02800.
@article{osti_1576520,
title = {Mechanistic Aspects of a Surface Organovanadium(III) Catalyst for Hydrocarbon Hydrogenation and Dehydrogenation},
author = {Kaphan, David M. and Ferrandon, Magali S. and Langeslay, Ryan R. and Celik, Gokhan and Wegener, Evan C. and Liu, Cong and Niklas, Jens and Poluektov, Oleg G. and Delferro, Massimiliano},
abstractNote = {Understanding the mechanisms of action for base metal catalysis of transformations typically associated with precious metals is essential for the design of technologies for a sustainable energy economy. Isolated transition-metal and post-transition-metal catalysts on oxides such as silica are generally proposed to effect hydrogenation and dehydrogenation by a mechanism featuring either σ-bond metathesis or heterolytic bond cleavage as the key bond activation step. In this work, an organovanadium(III) complex on silica, which is a precatalyst for both olefin hydrogenation and alkane dehydrogenation, is interrogated by a series of reaction kinetics and isotopic labeling studies in order to shed light on the operant mechanism for hydrogenation. The kinetic dependencies of the reaction components are potentially consistent with both the σ-bond metathesis and the heterolytic bond activation mechanisms; however, a key deuterium incorporation experiment definitively excludes the simple σ-bond metathesis mechanism. Alternatively, a two-electron redox cycle, rarely invoked for homologous catalyst systems, is also consistent with experimental observations. Evidence supporting the formation of a persistent vanadium(III) hydride upon hydrogen treatment of the as-prepared material is also presented.},
doi = {10.1021/acscatal.9b02800},
journal = {ACS Catalysis},
number = 12,
volume = 9,
place = {United States},
year = {2019},
month = {10}
}

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This content will become publicly available on October 28, 2020
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