Ligand effects on the electrochemical behavior of [Fe2(CO)5(L){μ-(SCH2)2(Ph)PO}] (L = PPh3, P(OEt)3) hydrogenase model complexes

Abstract

In this paper we study the influence of substituting one CO ligand in [Fe₂(CO)₆{μ-(SCH₂)₂(Ph)PO}] (1) by better σ-donor L ligands affording [Fe₂(CO)₅(L){μ-(SCH₂)₂(Ph)PO}] {L = PPh₃ (2) and P(OEt)₃ (3)} in relation to the steric interactions and the voltammetric behavior. Cyclic voltammetric investigations under N₂ and CO showed remarkable differences in the electrochemical behaviour of complexes 2 and 3: (i) Complex 2 tends to expel PPh₃ upon reduction whereas complex 3 exhibits chemical reversibility and (ii) Under CO, complex 3 reacts with CO affording a new compound P, which shows a reversible wave at E_1/2 ∼ −0.9 V (vs. ferrocenium/ferrocene couple). The presence of CO assists the formation of 1 after electrochemically induced loss of PPh₃ during the voltammetric experiment of 2. Using DFT calculations we provide an explanation for the difference in stabilities between the Fe–PPh₃ and Fe–P(OEt)₃ bonds.