UC Berkeley

Copyright © 2018 American Chemical Society. 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.