Phenyl-functionalized diiron propanediselenolato complexes containing the chelated or bridged 1,3-bis(diphenylphosphine)propane ligand

AbstractReaction of precursor Fe2[(μ-SeCH2)2CHC6H5](CO)6 (A) with 1,3-bis(diphenylphosphine)propane (dppp) in refluxing xylene yielded one diphosphine-containing complex Fe2[(μ-SeCH2)2CHC6H5](CO)4(κ2-dppp) (1) with the diphosphine of dppp displacing the apical and one basal carbonyl ligands of a single iron center, while treatment of precursor A with one-half equivalent of dppp in MeCN in the presence of Me3NO·2H2O gave another diphosphine-containing complex {Fe2[(μ-SeCH2)2CHC6H5](CO)5}2(μ,κ1,κ1-dppp) (2) with the diphosphine of the dppp bridging two diiron diselenolato clusters upon replacing one of basal carbonyls, respectively. The structures of both complexes were fully characterized by spectroscopic methods and X-ray crystallography. The electrochemical behaviors of both complexes were investigated by cyclic voltammetry (CV) and the electrochemical reduction of protons from acetic acid to give dihydrogen catalyzed by complex Fe2[(μ-SeCH2)2CHC6H5](CO)4(κ2-dppp) was observed.