Journal
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
Volume 9, Issue 14, Pages 3814-3818Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acs.jpclett.8b01710
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- Office of Science, Office of Basic Energy Sciences, Chemical Sciences Division of the U.S. Department of Energy [DE-10AC02-05CH11231]
- Office of Science of the U.S. Department of Energy [DE-AC02-05CH11231]
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Tetrahedral assemblies of stoichiometry M4L6 have 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.
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