Abstract

Transition metal catalysis hinges on the formation of metal-carbon bonds during catalytic cycles. the stability and reactivity of these bonds are what determine product chemo-, regio-, and enantioselectivity. the advent of electro synthetic methodologies has placed the current understanding of these metal-alkyl bonds into a new environment of charged species and electrochemically induced reactivity. in this paper, we explore the often-neglected impact of supporting electrolyte on homogeneous electrocatalytic mechanisms using the catalytic reduction of benzyl chlorides via Co and Fe tetraphenyl porphyrins as a model reaction. the mechanism of this reaction is confirmed to proceed through the formation of the metal-alkyl intermediates. Critically, the stability of these intermediates, in both the Co and Fe systems, is found to be affected by the hydrodynamic radius of the supporting electrolyte, leading to differences in electrolyte-solvent shell. These studies provide important information for the design of electro synthetic reactions and provide a starting point for the rational design of functional supporting electrolytes.

Department(s)

Chemistry

Comments

NSF Center for Synthetic Organic Electrochemistry, University of Utah, Grant CHE-2002158

International Standard Serial Number (ISSN)

1364-5498; 1359-6640

Document Type

Article - Journal

Document Version

Citation

File Type

text

Language(s)

English

Rights

© 2025 Royal Society of Chemistry, All rights reserved.

Publication Date

11 May 2023

PubMed ID

37489255

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Chemistry Commons

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