Contribution à l’etude de la réaction de substitution de carbonyles dans des complexes [Fe-Fe] modèle d’hydrogénases.

Abstract

This thesis concerns the synthesis and the structural characterization of organometallic complexes inspired by the active site of [Fe-Fe] hydrogenases. During this work, we have obtained:  Two binuclear hexacarbonyl complexes resulting from the reaction of nonacarbonyl iron Fe2(CO)9 on the phenyldithiobenzoate and 1,2- dithiolene respectively: - (µ-η2PhC(S)=C(S)Ph)Fe2(CO)6 1 - (µ-(o)SPhS-)Fe2(CO)6 2  Three complexes resulting from the substitution reaction of carbonyls by P(OMe)3 in complex 1: - (µPhC(S)=C(S)Ph)Fe2(CO)4[P(OMe)3]21a. - (η2PhC(S)=C(S)Ph)Fe(CO)[P(OMe)3]21b. - (µ-PhC(S)=C(S)Ph)Fe2(CO)5[P(OMe)3] 1c.  Two complexes resulting from the reaction of carbonyl substitution by (Me)2PhNC in complex 2: - (-(o)SPhS-)Fe2(CO)5[(Me)2PhNC] 2a. - (-(o)SPhS-)Fe2(CO)4[(Me)2PhNC]2 2b. The structural study of complexes 1, 1a, 2 and 2a shows that they are structural models of [Fe-Fe] hydrogenases.