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Title: Interplay of water and a supramolecular capsule for catalysis of reductive elimination reaction from gold

Abstract

Supramolecular assemblies have gained tremendous attention due to their ability to catalyze reactions with the efficiencies of natural enzymes. Using ab initio molecular dynamics, we identify the origin of the catalysis by the supramolecular capsule Ga4L612- on the reductive elimination reaction from gold complexes and assess their similarity to natural enzymes. By comparing the free energies of the reactants and transition states for the catalyzed and uncatalyzed reactions, we determine that an encapsulated water molecule generates electric fields that contributes the most to the reduction in the activation free energy. Although this is unlike the biomimetic scenario of catalysis through direct host-guest interactions, the electric fields from the nanocage also supports the transition state to complete the reductive elimination reaction with greater catalytic efficiency. However it is also shown that the nanocage poorly organizes the interfacial water, which in turn creates electric fields that misalign with the breaking bonds of the substrate, thus identifying new opportunities for catalytic design improvements in nanocage assemblies.

Authors:
 [1];  [1]; ORCiD logo [1]
  1. Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States); Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Publication Date:
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:
1599849
Grant/Contract Number:  
[AC02-05CH11231]
Resource Type:
Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
[ Journal Volume: 11; Journal Issue: 1]; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; molecular capsules; reaction mechanisms

Citation Formats

Welborn, Valerie Vaissier, Li, Wan-Lu, and Head-Gordon, Teresa. Interplay of water and a supramolecular capsule for catalysis of reductive elimination reaction from gold. United States: N. p., 2020. Web. doi:10.1038/s41467-019-14251-6.
Welborn, Valerie Vaissier, Li, Wan-Lu, & Head-Gordon, Teresa. Interplay of water and a supramolecular capsule for catalysis of reductive elimination reaction from gold. United States. doi:10.1038/s41467-019-14251-6.
Welborn, Valerie Vaissier, Li, Wan-Lu, and Head-Gordon, Teresa. Tue . "Interplay of water and a supramolecular capsule for catalysis of reductive elimination reaction from gold". United States. doi:10.1038/s41467-019-14251-6. https://www.osti.gov/servlets/purl/1599849.
@article{osti_1599849,
title = {Interplay of water and a supramolecular capsule for catalysis of reductive elimination reaction from gold},
author = {Welborn, Valerie Vaissier and Li, Wan-Lu and Head-Gordon, Teresa},
abstractNote = {Supramolecular assemblies have gained tremendous attention due to their ability to catalyze reactions with the efficiencies of natural enzymes. Using ab initio molecular dynamics, we identify the origin of the catalysis by the supramolecular capsule Ga4L612- on the reductive elimination reaction from gold complexes and assess their similarity to natural enzymes. By comparing the free energies of the reactants and transition states for the catalyzed and uncatalyzed reactions, we determine that an encapsulated water molecule generates electric fields that contributes the most to the reduction in the activation free energy. Although this is unlike the biomimetic scenario of catalysis through direct host-guest interactions, the electric fields from the nanocage also supports the transition state to complete the reductive elimination reaction with greater catalytic efficiency. However it is also shown that the nanocage poorly organizes the interfacial water, which in turn creates electric fields that misalign with the breaking bonds of the substrate, thus identifying new opportunities for catalytic design improvements in nanocage assemblies.},
doi = {10.1038/s41467-019-14251-6},
journal = {Nature Communications},
number = [1],
volume = [11],
place = {United States},
year = {2020},
month = {1}
}

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