Synthesis And Characterization Of Model Complexes Of [FeFe]-hydrogenase And Their Protonating, Electrochemical Investigations

This dissertation comprises mainly two aspects.1. Two bidentate phosphine ligands (PNP): (Ph₂P)₂NCH₂(2-C₅H₄N)(L¹), (Ph₂P)₂NCH₂Ph(L²)and two di-iron hexacarbonyl were synthesized: [Fe₂{(SCH₂)₂C(CH₃)(CH₂OH)}(CO)₆](6) and [Fe₂{(SCH₂)₂C(CH₃)(CH₂OTs)}(CO)₆] (7). The reactions of PNP ligands (L¹, L²) with the complexes 6 and 7 produced three di-iron tetracarbonyl complexes as models for the di-iron sub-unit of [FeFe]-hydrogenase: [Fe₂(SCH₂)₂C(Me)(CH₂OR)(PNP)(CO)₄] (R = H and PNP = L¹: 8; R = H and PNP = L²:9; R = Ts and PNP = L¹:10). Related di-iron complexes and organic compounds were fully characterized by using a variety of spectroscopic techniques, for example, FTIR, NMR and electrochemistry. The structure of the complex 10 was crystallographically determined. Protonation and electrochemistry including their catalytic reduction of proton for the complexes 8-10 were also investigated.2. The reactions of PNP ligands (L¹) with a series of di-iron hexacarbonyl complexes were preliminarily investi gated.