The quest for efficient and Earth Abundant Metal catalysts for electrochemical proton-reduction reactions has been invigorated by the understanding provided in the bimetallic active sites of [FeFe]- and [NiFe]-hydrogenase. Specifically, Nature’s way of achieving 2-electron processes from Earth Abundant Metals that match the efficiency of rare metals, such as platinum, appears to lie in the assembly of two metals in order to share the burden of redox changes. Alternatively, redox-active pendant units such as iron-sulfur clusters are expected to buffer the charge changes. This lecture will describe synthetic approaches to a matrix of thiolate-bridged Fe-Fe’, Fe-Ni, and Ni-Ni’ bimetallics in which the redox non-innocent NO ligands, and dithiolenes, are intimately involved with electrochemistry typically ascribed to metal centers. Mechanistic interpretation of electrochemical events in systems that lack hard amines find a role for hemi-lability of bridging thiolates as proton shuttles in the ultimate transfer of protons to an open site on Fe.

Abiotic ligands in sulfur-bridged NiFe and FeFe’ complexes as electrocatalysts for the HER: In search of hydrides and pendant bases

ACS Spring 2022

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.