Rhodium bis(quinolinyl)benzene complexes for methane activation and functionalization

Ross Fu; Matthew E. O'Reilly; Robert J. Nielsen; William A. Goddard; T. Brent Gunnoe

doi:10.1002/chem.201405460

Rhodium bis(quinolinyl)benzene complexes for methane activation and functionalization

Ross Fu, Matthew E. O'Reilly, Robert J. Nielsen, William A. Goddard, T. Brent Gunnoe

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

Abstract

A series of rhodium(III) bis(quinolinyl)benzene (bisq^x) complexes was studied as candidates for the homogeneous partial oxidation of methane. Density functional theory (DFT) (M06 with Poisson continuum solvation) was used to investigate a variety of (bisq^x) ligand candidates involving different functional groups to determine the impact on Rh^III(bisq^x)-catalyzed methane functionalization. The free energy activation barriers for methane C-H activation and Rh-methyl functionalization at 298 K and 498 K were determined. DFT studies predict that the best candidate for catalytic methane functionalization is Rh^III coordinated to unsubstituted bis(quinolinyl)benzene (bisq). Support is also found for the prediction that the η²-benzene coordination mode of (bisq^x) ligands on Rh encourages methyl group functionalization by serving as an effective leaving group for S_N2 and S_R2 attack.

Original language	English
Pages (from-to)	1286-1293
Number of pages	8
Journal	Chemistry - A European Journal
Volume	21
Issue number	3
DOIs	https://doi.org/10.1002/chem.201405460
Publication status	Published - 12 Jan 2015
Externally published	Yes

Keywords

Ab initio calculations
C-H activation
Catalysis
Methane functionalization
Rhodium

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10.1002/chem.201405460

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title = "Rhodium bis(quinolinyl)benzene complexes for methane activation and functionalization",

abstract = "A series of rhodium(III) bis(quinolinyl)benzene (bisqx) complexes was studied as candidates for the homogeneous partial oxidation of methane. Density functional theory (DFT) (M06 with Poisson continuum solvation) was used to investigate a variety of (bisqx) ligand candidates involving different functional groups to determine the impact on RhIII(bisqx)-catalyzed methane functionalization. The free energy activation barriers for methane C-H activation and Rh-methyl functionalization at 298 K and 498 K were determined. DFT studies predict that the best candidate for catalytic methane functionalization is RhIII coordinated to unsubstituted bis(quinolinyl)benzene (bisq). Support is also found for the prediction that the η2-benzene coordination mode of (bisqx) ligands on Rh encourages methyl group functionalization by serving as an effective leaving group for SN2 and SR2 attack.",

keywords = "Ab initio calculations, C-H activation, Catalysis, Methane functionalization, Rhodium",

author = "Ross Fu and O'Reilly, \{Matthew E.\} and Nielsen, \{Robert J.\} and Goddard, \{William A.\} and Gunnoe, \{T. Brent\}",

note = "Publisher Copyright: {\textcopyright} 2015 Wiley-VCH Verlag GmbH \& Co. KGaA.",

year = "2015",

month = jan,

day = "12",

doi = "10.1002/chem.201405460",

language = "English",

volume = "21",

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journal = "Chemistry - A European Journal",

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TY - JOUR

T1 - Rhodium bis(quinolinyl)benzene complexes for methane activation and functionalization

AU - Fu, Ross

AU - O'Reilly, Matthew E.

AU - Nielsen, Robert J.

AU - Goddard, William A.

AU - Gunnoe, T. Brent

PY - 2015/1/12

Y1 - 2015/1/12

N2 - A series of rhodium(III) bis(quinolinyl)benzene (bisqx) complexes was studied as candidates for the homogeneous partial oxidation of methane. Density functional theory (DFT) (M06 with Poisson continuum solvation) was used to investigate a variety of (bisqx) ligand candidates involving different functional groups to determine the impact on RhIII(bisqx)-catalyzed methane functionalization. The free energy activation barriers for methane C-H activation and Rh-methyl functionalization at 298 K and 498 K were determined. DFT studies predict that the best candidate for catalytic methane functionalization is RhIII coordinated to unsubstituted bis(quinolinyl)benzene (bisq). Support is also found for the prediction that the η2-benzene coordination mode of (bisqx) ligands on Rh encourages methyl group functionalization by serving as an effective leaving group for SN2 and SR2 attack.

AB - A series of rhodium(III) bis(quinolinyl)benzene (bisqx) complexes was studied as candidates for the homogeneous partial oxidation of methane. Density functional theory (DFT) (M06 with Poisson continuum solvation) was used to investigate a variety of (bisqx) ligand candidates involving different functional groups to determine the impact on RhIII(bisqx)-catalyzed methane functionalization. The free energy activation barriers for methane C-H activation and Rh-methyl functionalization at 298 K and 498 K were determined. DFT studies predict that the best candidate for catalytic methane functionalization is RhIII coordinated to unsubstituted bis(quinolinyl)benzene (bisq). Support is also found for the prediction that the η2-benzene coordination mode of (bisqx) ligands on Rh encourages methyl group functionalization by serving as an effective leaving group for SN2 and SR2 attack.

KW - Ab initio calculations

KW - C-H activation

KW - Catalysis

KW - Methane functionalization

KW - Rhodium

U2 - 10.1002/chem.201405460

DO - 10.1002/chem.201405460

M3 - Article

AN - SCOPUS:84920861509

SN - 0947-6539

VL - 21

SP - 1286

EP - 1293

JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

IS - 3

ER -

Rhodium bis(quinolinyl)benzene complexes for methane activation and functionalization

Abstract

Keywords

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