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; Mu Jeng Cheng; Robert J. Nielsen

doi:10.1021/acscatal.6b02781

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
, Mu Jeng Cheng
, Robert J. Nielsen

California Institute of Technology

Research output: Contribution to journal › Article › peer-review

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 density functional theory (DFT) study to predict that the barrier for (OPO)V to activate the secondary hydrogen of propane is ΔG^‡ = 25.2 kcal/mol at 298 K, 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 298 K. We conclude that (OPO)V represents a promising homogeneous catalyst for the monoxygenation of propane and other alkanes (including ethane), warranting experimental validation.

Original language	English
Pages (from-to)	356-364
Number of pages	9
Journal	ACS Catalysis
Volume	7
Issue number	1
DOIs	https://doi.org/10.1021/acscatal.6b02781
Publication status	Published - 6 Jan 2017
Externally published	Yes

Keywords

alkane C-H activation
alkane oxidation
density functional theory
homogeneous catalysis
pincer ligand
vanadium

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10.1021/acscatal.6b02781

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title = "Computational Design of a Pincer Phosphinito Vanadium ((OPO)V) Propane Monoxygenation Homogeneous Catalyst Based on the Reduction-Coupled Oxo Activation (ROA) Mechanism",

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 density functional theory (DFT) study to predict that the barrier for (OPO)V to activate the secondary hydrogen of propane is ΔG‡ = 25.2 kcal/mol at 298 K, 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 298 K. We conclude that (OPO)V represents a promising homogeneous catalyst for the monoxygenation of propane and other alkanes (including ethane), warranting experimental validation.",

keywords = "alkane C-H activation, alkane oxidation, density functional theory, homogeneous catalysis, pincer ligand, vanadium",

author = "Ross Fu and Goddard, \{William A.\} and Cheng, \{Mu Jeng\} and Nielsen, \{Robert J.\}",

note = "Publisher Copyright: {\textcopyright} 2016 American Chemical Society.",

year = "2017",

month = jan,

day = "6",

doi = "10.1021/acscatal.6b02781",

language = "English",

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T1 - Computational Design of a Pincer Phosphinito Vanadium ((OPO)V) Propane Monoxygenation Homogeneous Catalyst Based on the Reduction-Coupled Oxo Activation (ROA) Mechanism

AU - Fu, Ross

AU - Goddard, William A.

AU - Cheng, Mu Jeng

AU - Nielsen, Robert J.

PY - 2017/1/6

Y1 - 2017/1/6

N2 - 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 density functional theory (DFT) study to predict that the barrier for (OPO)V to activate the secondary hydrogen of propane is ΔG‡ = 25.2 kcal/mol at 298 K, 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 298 K. We conclude that (OPO)V represents a promising homogeneous catalyst for the monoxygenation of propane and other alkanes (including ethane), warranting experimental validation.

AB - 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 density functional theory (DFT) study to predict that the barrier for (OPO)V to activate the secondary hydrogen of propane is ΔG‡ = 25.2 kcal/mol at 298 K, 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 298 K. We conclude that (OPO)V represents a promising homogeneous catalyst for the monoxygenation of propane and other alkanes (including ethane), warranting experimental validation.

KW - alkane C-H activation

KW - alkane oxidation

KW - density functional theory

KW - homogeneous catalysis

KW - pincer ligand

KW - vanadium

U2 - 10.1021/acscatal.6b02781

DO - 10.1021/acscatal.6b02781

M3 - Article

AN - SCOPUS:85019666429

SN - 2155-5435

VL - 7

SP - 356

EP - 364

JO - ACS Catalysis

JF - ACS Catalysis

IS - 1

ER -

Computational Design of a Pincer Phosphinito Vanadium ((OPO)V) Propane Monoxygenation Homogeneous Catalyst Based on the Reduction-Coupled Oxo Activation (ROA) Mechanism

Abstract

Keywords

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