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Influence of bidentate phosphine ligands on the chemistry of [FeFe]‐hydrogenase model: insight into molecular structures and electrochemical characteristics
Author(s) -
Elkhateeb Mohammad,
AbulFutouh Hassan,
Alshurafa Hadil,
Görls Helmar,
Weigand Wolfgang
Publication year - 2020
Publication title -
applied organometallic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.53
H-Index - 71
eISSN - 1099-0739
pISSN - 0268-2605
DOI - 10.1002/aoc.5940
Subject(s) - chemistry , ferrocene , denticity , phosphine , ligand (biochemistry) , intramolecular force , medicinal chemistry , electrochemistry , substitution reaction , acetylene , acetonitrile , hydrogenase , chelation , carbon 13 nmr , stereochemistry , catalysis , crystal structure , crystallography , inorganic chemistry , organic chemistry , biochemistry , receptor , electrode
Substitution of carbonyl ligands of the hydrogenase model complex [Fe 2 (μ‐SeCH 2 CH(Me)CH 2 Se‐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 [Fe 2 {μ‐SeCH 2 CH(Me)CH 2 Se‐μ}(CO) 4 {μ,κ 1 ,κ 1 (P , P)‐dppf}] ( 1 ), while the dppac‐reaction produces an intermolecular bridged tetra‐iron model [Fe 2 {μ‐SeCH 2 CH(Me)CH 2 Se‐μ}(CO) 5 ] 2 {μ,κ 1 ,κ 1 (P,P)‐dppac} ( 2 ). However, the dppbz‐reaction gives [Fe 2 {μ‐SeCH 2 CH(Me)CH 2 Se‐μ}(CO) 4 {κ 2 (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, 1 H‐, 13 C{H}‐, 31 P{H}‐, 77 Se{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 CH 2 Cl 2 .