The discovery of ferrocene over 65 years ago sparked a revolution in organometallic chemistry that has shaped contemporary science. Although the +2 and +3 oxidation states are ubiquitous for ferrocene and its derivatives, the +4 oxidation state was only disclosed for the decamethylferrocene dication in 2016, and examples in the +1 oxidation state have not been isolated to date. Here we report the isolation and structural characterization of substituted 3d metallocene monoanions, [MI(CpR)2]- (M = Mn, Fe, Co), by potassium graphite reduction of respective [MII(CpR)2] precursors . Remarkably, these derivatized metallocenates contain 3d metals in formal +1 oxidation states, whilst electrochemical studies have revealed that the MII/MI reduction wave is reversible. Spectroscopic, magnetic and computational studies have been performed to probe the electronic structures of MI metallocene anions; we find that their electronic configurations are not as straighforward as one would predict based upon well-understood MII metallocenes. LA-UR-19-22448

Introducing the +1 oxidation state for derivatized 3d metallocene monoanions

2019 Fall National Meeting

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