title: Synthetic and structural studies on new diiron azadithiolate (ADT)-type model compounds for active site of [FeFe]hydrogenases.
abstract: A series of new diiron azadithiolate (ADT) complexes (1-8), which could be regarded as the active site models of [FeFe]hydrogenases, have been synthesized starting from parent complex [(μ-SCH(2))(2)NCH(2)CH(2)OH]Fe(2)(CO)(6) (A). Treatment of A with ethyl malonyl chloride or malonyl dichloride in the presence of pyridine afforded the malonyl-containing complexes [(μ-SCH(2))(2)NCH(2)CH(2)O(2)CCH(2)CO(2)Et]Fe(2)(CO)(6) (1) and [Fe(2)(CO)(6)(μ-SCH(2))(2)NCH(2)CH(2)O(2)C](2)CH(2) (2). Further treatment of 1 and 2 with PPh(3) under different conditions produced the PPh(3)-substituted complexes [(μ-SCH(2))(2)NCH(2)CH(2)O(2)CCH(2)CO(2)Et]Fe(2)(CO)(5)(PPh(3)) (3), [(μ-SCH(2))(2)NCH(2)CH(2)O(2)CCH(2)CO(2)Et]Fe(2)(CO)(4)(PPh(3))(2) (4), and [Fe(2)(CO)(5)(PPh(3))(μ-SCH(2))(2)NCH(2)CH(2)O(2)C](2)CH(2) (5). More interestingly, complexes 1-3 could react with C(60) in the presence of CBr(4) and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) via Bingel-Hirsch reaction to give the C(60)-containing complexes [(μ-SCH(2))(2)NCH(2)CH(2)O(2)CC(C(60))CO(2)Et]Fe(2)(CO)(6) (6), [Fe(2)(CO)(6)(μ-SCH(2))(2)NCH(2)CH(2)O(2)C](2)C(C(60)) (7), and [(μ-SCH(2))(2)NCH(2)CH(2)O(2)CC(C(60))CO(2)Et]Fe(2)(CO)(5)(PPh(3)) (8). The new ADT-type models 1-8 were characterized by elemental analysis and spectroscopy, whereas 2-4 were further studied by X-ray crystallography and 6-8 investigated in detail by DFT methods.
authors.affiliation: State Key Laboratory of Elemento-Organic Chemistry, College of Chemistry, Nankai University, Tianjin, 30007, China. lcsong@nankai.edu.cn
authors.forename: Li-Cheng
authors.initials: LC
authors.lastname: Song
authors.forename: Zhao-Jun
authors.initials: ZJ
authors.lastname: Xie
authors.forename: Xu-Feng
authors.initials: XF
authors.lastname: Liu
authors.forename: Jiang-Bo
authors.initials: JB
authors.lastname: Ming
authors.forename: Jian-Hua
authors.initials: JH
authors.lastname: Ge
authors.forename: Xiao-Guang
authors.initials: XG
authors.lastname: Zhang
authors.forename: Tian-Ying
authors.initials: TY
authors.lastname: Yan
authors.forename: Peng
authors.initials: P
authors.lastname: Gao
mesh_terms: D001372:Aza Compounds / Q000737:chemistry*; D020134:Catalytic Domain; D056831:Coordination Complexes / Q000138:chemical synthesis* / Q000737:chemistry / Q000494:pharmacology; D018360:Crystallography, X-Ray; D037741:Fullerenes / Q000737:chemistry; D006864:Hydrogenase / Q000737:chemistry* / Q000378:metabolism; D007501:Iron / Q000737:chemistry*; D007506:Iron-Sulfur Proteins / Q000737:chemistry* / Q000378:metabolism; D008958:Models, Molecular; D008968:Molecular Conformation
chemical_list: D001372:Aza Compounds; D056831:Coordination Complexes; D037741:Fullerenes; D007506:Iron-Sulfur Proteins; D007501:Iron; C118830:iron hydrogenase; D006864:Hydrogenase; C069837:fullerene C60