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Computational design of a pincer phosphinito vanadium ((OPO)V) propane monoxygenation homogeneous catalyst based on the reduction-coupled oxo activation (ROA) mechanism

Fu, Ross and Goddard, William A., III and Cheng, Mu-Jeng and Nielsen, Robert J. (2017) Computational design of a pincer phosphinito vanadium ((OPO)V) propane monoxygenation homogeneous catalyst based on the reduction-coupled oxo activation (ROA) mechanism. ACS Catalysis, 7 (1). pp. 356-364. ISSN 2155-5435. https://resolver.caltech.edu/CaltechAUTHORS:20161129-090636992

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Abstract

We propose the vanadium bis(2-phenoxyl)phosphinite pincer complex, denoted (OPO)V, as a low temperature water-soluble catalyst for monoxygenation of propane to isopropanol with functionalization and catalyst regeneration using molecular oxygen. We use DFT study to predict that the barrier for (OPO)V to activate the secondary hydrogen of propane is ΔG‡ = 25.2 kcal/mol at 298K, leading to isopropanol via the new reduction-coupled oxo activation (ROA) mechanism. We then show that reoxidation by dioxygen to complete the cycle is also favorable with ΔG‡ = 6.2 kcal/mol at 298K. We conclude that (OPO)V represents a promising homogeneous catalyst for the monoxygenation of propane and other alkanes (including ethane), warranting experimental validation.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/acscatal.6b02781DOIArticle
http://pubs.acs.org/doi/abs/10.1021/acscatal.6b02781PublisherArticle
http://pubs.acs.org/doi/suppl/10.1021/acscatal.6b02781PublisherSupporting Information
ORCID:
AuthorORCID
Goddard, William A., III0000-0003-0097-5716
Cheng, Mu-Jeng0000-0002-8121-0485
Nielsen, Robert J.0000-0002-7962-0186
Additional Information:© 2016 American Chemical Society. Received: September 29, 2016; Revised: November 16, 2016; Published: November 28, 2016. This research was supported by NSF (CHE-1214158).
Funders:
Funding AgencyGrant Number
NSFCHE-1214158
Subject Keywords:Homogeneous catalysis, pincer ligand, alkane C–H activation, density functional theory, vanadium, alkane oxidation
Issue or Number:1
Record Number:CaltechAUTHORS:20161129-090636992
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20161129-090636992
Official Citation:Computational Design of a Pincer Phosphinito Vanadium ((OPO)V) Propane Monoxygenation Homogeneous Catalyst Based on the Reduction-Coupled Oxo Activation (ROA) Mechanism Ross Fu, William A. Goddard, III, Mu-Jeng Cheng, and Robert J. Nielsen ACS Catalysis 2017 7 (1), 356-364 DOI: 10.1021/acscatal.6b02781
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:72366
Collection:CaltechAUTHORS
Deposited By: Ruth Sustaita
Deposited On:29 Nov 2016 17:16
Last Modified:03 Oct 2019 16:17

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