Electrostatics Generated by a Supramolecular Capsule Stabilizes the Transition State for Carbon–Carbon Reductive Elimination from Gold(III) Complex

doi:10.1021/acs.jpclett.8b01710

Title: Electrostatics Generated by a Supramolecular Capsule Stabilizes the Transition State for Carbon–Carbon Reductive Elimination from Gold(III) Complex

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Abstract

Tetrahedral assemblies of stoichiometry M ₄L ₆have been proven to catalyze a range of chemical reactions including the carbon-carbon reductive elimination reaction from transition metals such as gold. Here, we perform quantum chemical calculations of Gold(III) transition metal complexes in vacuum, and encapsulated in Ga ₄L ₆ ^12- or Si ₄L ₆ ^8- assemblies within both a reaction field continuum solvent and in an aqueous molecular environment with counterions, to rationalize the rate enhancements observed experimentally for the reductive elimination reaction. We find that the Ga ₄L ₆ ^12- assembly lowers the energy barrier of the reaction compared to Si ₄L ₆ ^8-, which is consistent with kinetic trends observed experimentally. We have determined that the primary factor for catalytic rate acceleration stems from the electrostatic environment emanating from the Ga ₄L ₆ ^12- capsule as opposed to the water or counterions.

Authors:

^[1];

^[1]

Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Sciences Division

Publication Date:: 2018-06-25

Research Org.:: Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

OSTI Identifier:: 1532332

Grant/Contract Number:: AC02-05CH11231

Resource Type:: Journal Article: Accepted Manuscript

Journal Name:: Journal of Physical Chemistry Letters

Additional Journal Information:: Journal Volume: 9; Journal Issue: 14; Journal ID: ISSN 1948-7185

Publisher:: American Chemical Society

Country of Publication:: United States

Language:: English

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

Citation Formats


                    Vaissier Welborn, Valerie, and Head-Gordon, Teresa. Electrostatics Generated by a Supramolecular Capsule Stabilizes the Transition State for Carbon–Carbon Reductive Elimination from Gold(III) Complex.  United States: N. p., 2018. 
        Web.  doi:10.1021/acs.jpclett.8b01710.

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                    Vaissier Welborn, Valerie, & Head-Gordon, Teresa. Electrostatics Generated by a Supramolecular Capsule Stabilizes the Transition State for Carbon–Carbon Reductive Elimination from Gold(III) Complex.  United States.  doi:10.1021/acs.jpclett.8b01710.

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                    Vaissier Welborn, Valerie, and Head-Gordon, Teresa. Mon .  
        "Electrostatics Generated by a Supramolecular Capsule Stabilizes the Transition State for Carbon–Carbon Reductive Elimination from Gold(III) Complex".  United States.  doi:10.1021/acs.jpclett.8b01710.  https://www.osti.gov/servlets/purl/1532332.

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@article{osti_1532332,

  title        = {Electrostatics Generated by a Supramolecular Capsule Stabilizes the Transition State for Carbon–Carbon Reductive Elimination from Gold(III) Complex},

  author       = {Vaissier Welborn, Valerie and Head-Gordon, Teresa},

  abstractNote = {Tetrahedral assemblies of stoichiometry M4L6have been proven to catalyze a range of chemical reactions including the carbon-carbon reductive elimination reaction from transition metals such as gold. Here, we perform quantum chemical calculations of Gold(III) transition metal complexes in vacuum, and encapsulated in Ga4L612- or Si4L68- assemblies within both a reaction field continuum solvent and in an aqueous molecular environment with counterions, to rationalize the rate enhancements observed experimentally for the reductive elimination reaction. We find that the Ga4L612- assembly lowers the energy barrier of the reaction compared to Si4L68-, which is consistent with kinetic trends observed experimentally. We have determined that the primary factor for catalytic rate acceleration stems from the electrostatic environment emanating from the Ga4L612- capsule as opposed to the water or counterions.},

  doi          = {10.1021/acs.jpclett.8b01710},

  journal      = {Journal of Physical Chemistry Letters},

  issn         = {1948-7185},

  number       = 14,

  volume       = 9,

  place        = {United States},

  year         = {2018},

  month        = {6}

}

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DOI: 10.1021/acs.jpclett.8b01710

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