A cross-metathesis approach for polymetallic [FeFe]-hydrogenase mimics.

A method has been developed for synthesizing [FeFe]-H 2 ase mimics with diverse structures and properties, employing cross-metathesis of olefins. Vinylmetallocenes (5 and 6) and vinyl half-sandwich complexes (10 and 11) have been used as cross-metathesis partners with [FeFe]-H 2 ase mimics (4, 8, and 9) bearing a double bond in the moiety attached to the ADT-bridge nitrogen. Electrochemical studies of these complexes, encompassing metallocene-type (7a-b, 12a-b, and 13a-b) as well as half-sandwich derivatives (12c and 13c-d), have demonstrated that the introduction of a redox unit has a marginal impact on the reduction potential of these [FeFe]-H 2 ase mimics. The application of this cross-metathesis approach has allowed the synthesis of [FeFe]-H 2 ase mimics featuring an Ir(III) electrochemical antenna (16-18) as well as systems having an electron-donor-photosensitizer structure (ED-PS) (23). The electrocatalytic properties of these complexes have been elucidated through electrochemical studies.