Directing protonation in [FeFe] hydrogenase active site models by modifications in their second coordination sphere

摘要

Subtle changes in the second coordination sphere of [Cl_2bdtFe_2-(CO)_4(Ph_2P-CH_2-X-CH_2-PPh_2)] (bdt = benzene-1,2-dithiolate, X = NCH_3, NCH_2CF_3, CH_2) that do not influence the electronic character of the Fe_2 center can however direct protonation to three different sites: the N in the bis-phosphane, the Fe-Fe bond or the bdt-S.