Pioneering Heterogeneous Organometallic-Mediated Electrocatalytic Reactions

Objetivo

This project pioneers the use of Heterogeneous Organometallic Mediated Electrocatalytic Reactions (HOMER) and our understanding thereof. Examples of electron transfer activation of C-H, C-Halide bonds and cycloaddition reactions of unactivated olefins are sought that are catalysed by appropriate combinations of electrochemically generated odd-electron (17-electron) organometallic “radical” complexes and 7-electron perhalogenated arylborane Lewis acidic radical species. The electrochemistry of a series of Group VI-IX transition metal half-sandwich complexes, empirically “Cp’M(CO)n” (where n=2 or 3 in order to satisfy the metal centre’s demand for an 18-electron configuration; Cp’ = η5-C5H4CO2R, where R = Me) will be explored both in the solution phase and covalently attached to an electrode surface. These chemically modified “HOMER platforms” will be exposed to a wide variety of hydrocarbon feedstocks during electrolysis, and evidence of C-H/C-halide bond activation sought. Optimization of the HOMER catalysts will be attempted by systematically varying the ligands within the complex.This includes a study of the electrochemistry of Group IV to VIII transition metal complexes bearing at least 1 borylcyclopentadienyl ligand that incorporates a Lewis acid group into the HOMER catalyst.
Novel perchlorinated arylboranes, (C6F5)3-nB(C6Cl5)n n=1-3 “BArCl” recently reported by the PI and co-workers will be examined for their activity in Frustrated Lewis Pair (FLP) activation of small molecules. An “electrochemical-FLP” (e-FLP) system will be pioneered by electrochemically oxidising the [BArClH]- products of FLP activation of H2 to produce [BArClH]• intermediates - a source of “H•”. The activation of small molecules via the e-FLP concept will be explored, and combined with suitable HOMER catalysts in an effort to generate e-FLP-HOMER systems capable of undergoing an electrocatalytic analogue of the Fischer-Tropsch reaction.

Ámbito científico

Régimen de financiación

ERC-SG - ERC Starting Grant

Institución de acogida

UNIVERSITY OF EAST ANGLIA

Aportación de la UE

€ 1 327 116,00

Dirección

EARLHAM ROAD
NR4 7TJ Norwich
Reino Unido

Región

East of England East Anglia Norwich and East Norfolk

Tipo de actividad

Higher or Secondary Education Establishments

Contacto administrativo

Chris Killen (Dr.)

Investigador principal

Gregory George Wildgoose (Dr.)

Enlaces

Contactar con la organización Sitio web

Coste total

Sin datos

Beneficiarios (1)