Mechanistic Studies of Single-Step Styrene Production Using a Rhodium(I) Catalyst

Vaughan, Benjamin A.; Khani, Sarah K.; Gary, J. Brannon; Kammert, James D.; Webster-Gardiner, Michael S.; McKeown, Bradley A.; Davis, Robert J.; Cundari, Thomas R.; Gunnoe, T. Brent

doi:10.1021/jacs.6b10658

Title: Mechanistic Studies of Single-Step Styrene Production Using a Rhodium(I) Catalyst

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Abstract

The direct and single-step conversion of benzene, ethylene, and a Cu(II) oxidant to styrene using the Rh(I) catalyst (^FlDAB)Rh(TFA)(η²-C₂H₄) [^FlDAB = N,N'-bis(pentafluorophenyl)-2,3-dimethyl-1,4-diaza-1,3-butadiene; TFA = trifluoroacetate] has been reported to give quantitative yields (with Cu(II) as the limiting reagent) and selectivity combined with turnover numbers >800. Our report details mechanistic studies of this catalytic process using a combined experimental and computational approach. Examining catalysis with the complex (^FlDAB)Rh(OAc)(η²-C₂H₄) shows that the reaction rate has a dependence on catalyst concentration between first- and half-order that varies with both temperature and ethylene concentration, a first-order dependence on ethylene concentration with saturation at higher concentrations of ethylene, and a zero-order dependence on the concentration of Cu(II) oxidant. The kinetic isotope effect was found to vary linearly with the order in (^FlDAB)Rh(OAc)(η²-C₂H₄), exhibiting no KIE when [Rh] was in the half-order regime, and a k_H/k_D value of 6.7(6) when [Rh] was in the first-order regime. From these combined experimental and computational studies, competing pathways, which involve all monomeric Rh intermediates and a binuclear Rh intermediate in the other case, are presented.

Authors:

^[1]; Khani, Sarah K. ^[2]; Gary, J. Brannon ^[2]; Kammert, James D. ^[1]; Webster-Gardiner, Michael S. ^[1]; McKeown, Bradley A. ^[1]; Davis, Robert J. ^[1]; Cundari, Thomas R. ^[2];

^[1]

Univ. of Virginia, Charlottesville, VA (United States)
Univ. of North Texas, Denton, TX (United States)

Publication Date:: Fri Jan 20 00:00:00 EST 2017

Research Org.:: Univ. of Virginia, Charlottesville, VA (United States); Univ. of North Texas, Denton, TX (United States)

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

OSTI Identifier:: 1605982

Grant/Contract Number:: SC0000776; FG02-03ER15387

Resource Type:: Accepted Manuscript

Journal Name:: Journal of the American Chemical Society

Additional Journal Information:: Journal Volume: 139; Journal Issue: 4; Journal ID: ISSN 0002-7863

Publisher:: American Chemical Society (ACS)

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats


                    Vaughan, Benjamin A., Khani, Sarah K., Gary, J. Brannon, Kammert, James D., Webster-Gardiner, Michael S., McKeown, Bradley A., Davis, Robert J., Cundari, Thomas R., and Gunnoe, T. Brent. Mechanistic Studies of Single-Step Styrene Production Using a Rhodium(I) Catalyst.  United States: N. p., 2017. 
Web.  doi:10.1021/jacs.6b10658.

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                    Vaughan, Benjamin A., Khani, Sarah K., Gary, J. Brannon, Kammert, James D., Webster-Gardiner, Michael S., McKeown, Bradley A., Davis, Robert J., Cundari, Thomas R., & Gunnoe, T. Brent. Mechanistic Studies of Single-Step Styrene Production Using a Rhodium(I) Catalyst.  United States.  https://doi.org/10.1021/jacs.6b10658

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                    Vaughan, Benjamin A., Khani, Sarah K., Gary, J. Brannon, Kammert, James D., Webster-Gardiner, Michael S., McKeown, Bradley A., Davis, Robert J., Cundari, Thomas R., and Gunnoe, T. Brent. Fri .  
"Mechanistic Studies of Single-Step Styrene Production Using a Rhodium(I) Catalyst".  United States.  https://doi.org/10.1021/jacs.6b10658.  https://www.osti.gov/servlets/purl/1605982.

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@article{osti_1605982,

  title        = {Mechanistic Studies of Single-Step Styrene Production Using a Rhodium(I) Catalyst},

  author       = {Vaughan, Benjamin A. and Khani, Sarah K. and Gary, J. Brannon and Kammert, James D. and Webster-Gardiner, Michael S. and McKeown, Bradley A. and Davis, Robert J. and Cundari, Thomas R. and Gunnoe, T. Brent},

  abstractNote = {The direct and single-step conversion of benzene, ethylene, and a Cu(II) oxidant to styrene using the Rh(I) catalyst (FlDAB)Rh(TFA)(η2-C2H4) [FlDAB = N,N'-bis(pentafluorophenyl)-2,3-dimethyl-1,4-diaza-1,3-butadiene; TFA = trifluoroacetate] has been reported to give quantitative yields (with Cu(II) as the limiting reagent) and selectivity combined with turnover numbers >800. Our report details mechanistic studies of this catalytic process using a combined experimental and computational approach. Examining catalysis with the complex (FlDAB)Rh(OAc)(η2-C2H4) shows that the reaction rate has a dependence on catalyst concentration between first- and half-order that varies with both temperature and ethylene concentration, a first-order dependence on ethylene concentration with saturation at higher concentrations of ethylene, and a zero-order dependence on the concentration of Cu(II) oxidant. The kinetic isotope effect was found to vary linearly with the order in (FlDAB)Rh(OAc)(η2-C2H4), exhibiting no KIE when [Rh] was in the half-order regime, and a kH/kD value of 6.7(6) when [Rh] was in the first-order regime. From these combined experimental and computational studies, competing pathways, which involve all monomeric Rh intermediates and a binuclear Rh intermediate in the other case, are presented.},

  doi          = {10.1021/jacs.6b10658},

  journal      = {Journal of the American Chemical Society},

  number       = 4,

  volume       = 139,

  place        = {United States},

  year         = {Fri Jan 20 00:00:00 EST 2017},

  month        = {Fri Jan 20 00:00:00 EST 2017}

}

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