Diiron models for the active site of Fe-only hydrogenase with terminal organosulfur ligation: synthesis, structures and electrochemistry.
Diiron model complexes (micro-SCH(2)CH(2)CH(2)S)Fe(2)(CO)(5)L with thioether-substitution, L=S(CH(2)CH(3))(2) (2), S(CH(2)CH(3))(CH(2)CH(2)Cl) (3), S(CH(2)CH(3))(C(6)H(5)) (4), or sulfoxide-substitution, L=SO(CH(2)CH(2)CH(3))(2) (5), SO(CH(3))(2) (6), were synthesized as active site analogues of Fe-only hydrogenase. The organosulfur ligands were introduced into the diiron centers via moderately stable intermediates following two routes. The X-ray crystallographic structures of complexes 2-6 show the apical positions of terminal organosulfur ligands. The electrochemical behaviors of the model complexes were investigated, especially for the interesting properties of the derivative of 6 which is proposed to be the first model with weak donor ligand similar to CO.
Hu
Ming-Qiang
MQ
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002, PR China.
Ma
Cheng-Bing
CB
Si
You-Tao
YT
Chen
Chang-Neng
CN
Liu
Qiu-Tian
QT
D001665:Binding Sites; D018360:Crystallography, X-Ray; D004563:Electrochemistry; D006864:Hydrogenase / Q000737:chemistry / Q000378:metabolism*; D007501:Iron / Q000737:chemistry*; D007506:Iron-Sulfur Proteins / Q000737:chemistry / Q000378:metabolism*; D008958:Models, Molecular; D019906:Nuclear Magnetic Resonance, Biomolecular; D011487:Protein Conformation; D017550:Spectroscopy, Fourier Transform Infrared; D013457:Sulfur Compounds / Q000138:chemical synthesis* / Q000737:chemistry
D007506:Iron-Sulfur Proteins; D013457:Sulfur Compounds; D007501:Iron; C118830:iron hydrogenase; D006864:Hydrogenase