Abstract
Substitution of carbonyl ligands of the hydrogenase model complex [Fe2(μ‐SeCH2CH(Me)CH2Se‐μ)(CO)6] (A), by 1,1′‐bis (diphenylphosphino)ferrocene (dppf), 1,2‐bis (diphenylphosphino)benzene (dppbz) or 1,2‐bis (diphenylphosphino)acetylene (dppac) is investigated. It is found that the reaction product depends on the diphosphine used. In the case of dppf, the product is an intramolecular bridged disubstituted complex [Fe2{μ‐SeCH2CH(Me)CH2Se‐μ}(CO)4{μ,κ1,κ1(P,P)‐dppf}] (1), while the dppac‐reaction produces an intermolecular bridged tetra‐iron model [Fe2{μ‐SeCH2CH(Me)CH2Se‐μ}(CO)5]2{μ,κ1,κ1(P,P)‐dppac} (2). However, the dppbz‐reaction gives [Fe2{μ‐SeCH2CH(Me)CH2Se‐μ}(CO)4{κ2(P,P)‐dppbz}] (3) in which the dppbz ligand is bonded to one Fe atom in a chelated manner. The newly prepared complexes (1–3) have been characterized by elemental analysis, IR, 1H‐, 13C{H}‐, 31P{H}‐, 77Se{H}‐NMR spectroscopy and X‐ray structure determination. The electrochemical behavior of 2 and 3, in absence and presence of acid, is described by cyclic voltammetric measurements in CH2Cl2.
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