Abstract
Multimetallic redox cooperativity features heavily in both bioinorganic and synthetic reactions. Here, the electronic structure of the bimetallic Ti/Ti complex 11, [(Cp(2)Ti)(2)(O(2)C(3)TMS(2))] has been revisited with EPR, confirming a predominantly Ti(III)/Ti(III) electronic structure. Reactions of 11 with 2,6-dimethylphenyl isocyanide (CNXyl), TMSCl, MeI, and BnCl were explored, revealing differential redox chemistry of the bimetallic core. In reactions with CNXyl and TMSCl, the metallacyclic Ti(III) center remained unperturbed, with reactions taking place at the pendent κ(2)(O,O)-titanocene fragment, while reaction with MeI resulted in remote oxidation of the metallacyclic Ti center, indicative of a cooperative redox process. All structures were studied via X-ray diffraction and EPR spectroscopic analysis, and their electronic structures are discussed in the context of the covalent bond classification (CBC) electron counting method.