Oxidative Addition of Thioesters to Iron(0): Active-Site Models for Hmd, Nature’s Third Hydrogenase

Abstract

The thioester Ph2PC6H4-2-C(O)SPh reacts with Fe2(CO)9 to give [Ph2PC6H4C(O)]Fe(SPh)(CO)3, a model for the CO-inhibited active site of the enzyme Hmd. This species, which reversibly decarbonylates to give a diiron derivative, reacts with cyanide to give [[Ph2PC6H4C(O)]Fe(SPh)(CN)(CO)2]−.