Preparation, structures and electrochemical property of phosphine substituted diiron azadithiolates relevant to the active site of Fe-only hydrogenases.
Mono- and di-phosphine diiron azadithiolate complexes [{(mu-SCH(2))(2)N(4-NO(2)C(6)H(4))}Fe(2)(CO)(5)(PMe(3))] (2), [{(mu-SCH(2))(2)N(4-NO(2)C(6)H(4))}{Fe(CO)(2)L}(2)] (3, L=PMe(3); 4, PMe(2)Ph) and the mu-hydride diiron complex [3(FeHFe)](+)[PF(6)](-) were prepared as biomimetic models of the active site of Fe-only hydrogenases. The complexes 2-4 and [3(FeHFe)](+)[PF(6)](-) were characterized by IR, (31)P, (1)H and (13)C NMR spectra and their molecular structures were determined by single crystal X-ray analyses. The PMe(3) ligand in complex 2 lies on the basal position. The PMe(3)-disubstituted complex 3 exists as two configuration isomers, transoid basal/basal and apical/basal, in the crystalline state, while two PMe(2)Ph ligands of 4 are in an apical/basal orientation. The variable temperature (31)P NMR spectra of 2 and 3 were made to have an insight into the existence of the possible conformation isomers of 2 and 3 in solution. The [3(FeHFe)](+) cation possesses the sole transoid ba/ba geometry as other reported mu-hydride diiron analogues. The electrocatalytic property of {(mu-SCH(2))(2)NC(6)H(5)}[Fe(CO)(2)PMe(3)](2) (5) was studied for proton reduction in the presence of HOAc.
Dong
Weibing
W
State Key Laboratory of Fine Chemicals, DUT-KTH Joint Education and Research Center on Molecular Devices, Dalian University of Technology (DUT), Dalian 116012, China.
Wang
Mei
M
Liu
Tianbiao
T
Liu
Xiaoyang
X
Jin
Kun
K
Sun
Licheng
L
D001372:Aza Compounds / Q000737:chemistry*; D001665:Binding Sites; D003013:Clostridium / Q000201:enzymology; D018360:Crystallography, X-Ray; D003901:Desulfovibrio / Q000201:enzymology; D004563:Electrochemistry; D005296:Ferrous Compounds; D006864:Hydrogenase / Q000737:chemistry*; D007506:Iron-Sulfur Proteins / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D008958:Models, Molecular; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry; D010720:Phosphines / Q000737:chemistry*
D001372:Aza Compounds; D005296:Ferrous Compounds; D007506:Iron-Sulfur Proteins; D009942:Organometallic Compounds; D010720:Phosphines; C118830:iron hydrogenase; D006864:Hydrogenase; C044646:phosphine