Opening up New Oxidation States in Metallocene Chemistry Across the Periodic Table

Lead Research Organisation: University of Manchester
Department Name: Chemistry

Abstract

Metallocenes are compounds that contain a metal atom sandwiched between two five-membered carbon rings, and are best exemplified by ferrocene, [Fe(C5H5)2]. The discovery of ferrocene over 65 years ago led to the award of the 1973 Nobel Prize in Chemistry and sparked a chemical revolution that has shaped contemporary science. Although the +2 and +3 oxidation states are ubiquitous for ferrocene and its derivatives, isolated +1 oxidation state complexes of the first row transition metals have proved difficult to access. The metallocene family of compounds are keystone molecules that have found application in diverse research areas and industrial applications. We anticipate that the targeted synthesis and study of metallocene anions will generate important new textbook data and open up numerous vistas for future exploration.

In this project, the student will first use anaerobic synthetic chemistry techniques to target the isolation of derivatised metallocene anions of the first row transition metals, where the metal is formally in the +1 oxidation state. We will investigate the reactivity profiles of these compounds, and we will interrogate their electronic structures with a plethora of spectroscopic techniques, magnetic measurements and high-level ab initio calculations. We will use these data to inform the expansion of this project so that the student can synthesise and study metallocene anions for metals across the Periodic Table. The results will provide new insights into the fundamentals of structure and bonding of the metallocene family, which underpin their versatile applications.

The project is focused in the synthetic coordination chemistry EPSRC research area, and analysis of the compounds made by the student is of relevance to other EPSRC research areas including chemical structure and computational and theoretical chemistry.

Publications

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Studentship Projects

Project Reference Relationship Related To Start End Student Name
EP/R513131/1 01/10/2018 30/09/2023
2297278 Studentship EP/R513131/1 16/09/2019 01/07/2023 Corentin Magnoux