title: A new cumulene diiron complex related to the active site of Fe-only hydrogenases and its phosphine substituted derivatives: synthesis, electrochemistry and structural characterization.
abstract: A new cumulene diiron complex related to the Fe-only hydrogenase active site [(μ-SCH(2)C(S)CCH(2))Fe(2)(CO)(6)] (1) was obtained by treatment of (μ-LiS)(2)Fe(2)(CO)(6) with excess 1,4-dichloro-2-butyne. By controllable CO displacement of 1 with PPh(3) and bis(diphenylphosphino)methane (dppm), mono- and di-substituted complexes, namely [(μ-SCH(2)C(S)CCH(2))Fe(2)(CO)(5)L] (2: L=PPh(3); 3: L=dppm) and [(μ-SCH(2)C(S)CCH(2))Fe(2)(CO)(4)L(2)] (4: L=PPh(3); 5: L=dppm) could be prepared in moderate yields. Treatment of 1 with bis(diphenylphosphino)ethane (dppe) afforded a double butterfly complex [(μ-SCH(2)C(S)CCH(2))Fe(2)(CO)(5)](2)(μ-dppe) (7). With dppm in refluxing toluene, a dppm-bridged complex [(μ-SCH(2)C(S)CCH(2))Fe(2)(CO)(4)(μ-dppm)] (6) was obtained. These model complexes were characterized by IR, (1)H, (31)P NMR spectra and the molecular structures of 1, 2 and 5-7 were determined by single crystal X-ray analyses. The electrochemistry of 1-3 was studied and the electrocatalytic property of 1 was investigated for proton reduction in the presence of HOAc.
authors.affiliation: State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002, PR China.
authors.forename: Na
authors.initials: N
authors.lastname: Wen
authors.forename: Fenfen
authors.initials: F
authors.lastname: Xu
authors.forename: Yanan
authors.initials: Y
authors.lastname: Feng
authors.forename: Shaowu
authors.initials: S
authors.lastname: Du
mesh_terms: D001665:Binding Sites; D020134:Catalytic Domain; D018360:Crystallography, X-Ray; D004563:Electrochemistry / Q000379:methods*; D006859:Hydrogen / Q000378:metabolism*; D006864:Hydrogenase / Q000032:analysis / Q000737:chemistry*; D007501:Iron / Q000737:chemistry / Q000378:metabolism; D007506:Iron-Sulfur Proteins / Q000032:analysis / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D008958:Models, Molecular; D009942:Organometallic Compounds / Q000032:analysis / Q000138:chemical synthesis; D010084:Oxidation-Reduction; D010720:Phosphines / Q000737:chemistry*; D011090:Polyenes / Q000032:analysis / Q000138:chemical synthesis; D013438:Sulfhydryl Compounds / Q000737:chemistry
chemical_list: D007506:Iron-Sulfur Proteins; D009942:Organometallic Compounds; D010720:Phosphines; D011090:Polyenes; D013438:Sulfhydryl Compounds; D006859:Hydrogen; D007501:Iron; C118830:iron hydrogenase; D006864:Hydrogenase