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

Abstract

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.

Authors:
ORCiD logo [1]; ORCiD logo [1]
  1. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Sciences Division
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1532332
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
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.
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.
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.
@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},
number = 14,
volume = 9,
place = {United States},
year = {2018},
month = {6}
}

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Works referencing / citing this record:

Gold‐Catalyzed Cross‐Coupling Reactions: An Overview of Design Strategies, Mechanistic Studies, and Applications
journal, December 2019


Interplay of water and a supramolecular capsule for catalysis of reductive elimination reaction from gold
journal, January 2020

  • Welborn, Valerie Vaissier; Li, Wan-Lu; Head-Gordon, Teresa
  • Nature Communications, Vol. 11, Issue 1
  • DOI: 10.1038/s41467-019-14251-6