title: Reactions of the cationic zinc thiolate model complex [Zn(Tab)4](PF6)2 with N-donor ligands and cobalt dichloride.
abstract: Reactions of [Zn(Tab)(4)](PF(6))(2) (Tab = 4-(trimethylammonio)benzenethiolate) (1) with 2,2'-bipyridine (2,2'-bipy), 1,10-phenanthroline (phen), 2,9-dimethyl-1,10-phenanthroline (2,9-dmphen), N-methylimidazole (N-Meim), and 2,6-bis(pyrazol-3-yl)pyridine (bppy) or with CoCl(2)·6H(2)O at the presence of N-donor ligands (2,2'-bipy, phen, 4,4'-dimethyl-2,2'-bipyridine (4,4'-dmbpy), 2,6-bis(3,5-dimethyl-1H-pyrazol-1-yl)pyridine (bdmppy))gave rise to a family of zinc or cobalt thiolate complexes, [Zn(Tab)(2)(L)](PF(6))(2) (2: L = 2,2'-bipy, 3: L = phen, 4: L = 2,9-dmphen), [Zn(Tab)(2)(N-Meim)(2)](PF(6))(2) (5), [Zn(Tab)(2)(bppy)](PF(6))(2) (6), [Co(Tab)(2)(L)(2)](PF(6))(3) (7: L = 2,2'-bipy, 8: L = phen, 9: L = 4,4'-dmbpy), and [Co(Tab)(bdmppy)Cl](PF(6)) (10). These compounds were characterized by elemental analysis, IR spectra, UV-vis spectra,(1)H NMR, electrospray ionization (ESI) mass spectra, and single-crystal X-ray diffraction. The Zn(II) in [Zn(Tab)(2)L(n)](2+)dications of 2-5 is tetrahedrally coordinated by two Tab ligands and one L or two N-Meim ligands. In 6, the Zn(II) has a distorted trigonal-bipyramidal geometry, coordinated by two Tab ligands and one tridentate bppy ligand. The Co(III) in the [Co(Tab)(2)(L)(2)](3+) trications of 7-9 is octahedraly chelated by two bidentate L ligands and two Tab ligands. In 10, the Co(II) adopts a distorted trigonal-bipyramidal geometry, coordinated by one Cl(-), one Tab ligand, and one tridentate bdmppy. In the formation of 2-6, two Tab ligands are removed from the [Zn(Tab)(4)](2+) dication when it is attacked by L ligands, while in the cases of 7-9, the Zn(II) of the [Zn(Tab)(4)](2+) dication was replaced by Co(III) (derived from oxidation of Co(II) by O(2)) followed by the removal of two Tab ligands via L ligands. In the case of 10, the central Zn(II) of the [Zn(Tab)(4)](2+) dication was displaced by Co(II) followed by the removal of three Tab ligands via one Cl(-) and one tridentate bdmppy. These ligand and metal replacement reactions may provide some interesting information on the interactions of the [Zn(S-Cys)(4)](2-) unit of Zn-MTs with N-heterocyclic ligands and toxic metal ions encountered in a natural environment.
authors.affiliation: College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, People's Republic of China.
authors.forename: Ai-Xia
authors.initials: AX
authors.lastname: Zheng
authors.forename: Jing
authors.initials: J
authors.lastname: Si
authors.forename: Xiao-Yan
authors.initials: XY
authors.lastname: Tang
authors.forename: Li-Li
authors.initials: LL
authors.lastname: Miao
authors.forename: Miao
authors.initials: M
authors.lastname: Yu
authors.forename: Kai-Peng
authors.initials: KP
authors.lastname: Hou
authors.forename: Fan
authors.initials: F
authors.lastname: Wang
authors.forename: Hong-Xi
authors.initials: HX
authors.lastname: Li
authors.forename: Jian-Ping
authors.initials: JP
authors.lastname: Lang
mesh_terms: D015082:2,2'-Dipyridyl / Q000737:chemistry; D003035:Cobalt / Q000737:chemistry*; D056831:Coordination Complexes / Q000737:chemistry*; D018360:Crystallography, X-Ray; D007093:Imidazoles / Q000737:chemistry; D008024:Ligands; D008958:Models, Molecular; D010618:Phenanthrolines / Q000737:chemistry; D011725:Pyridines / Q000737:chemistry; D013438:Sulfhydryl Compounds / Q000737:chemistry*; D015032:Zinc / Q000737:chemistry*
chemical_list: C560551:4,4'-dimethyl-2,2'-bipyridine; D056831:Coordination Complexes; D007093:Imidazoles; D008024:Ligands; D010618:Phenanthrolines; D011725:Pyridines; D013438:Sulfhydryl Compounds; D003035:Cobalt; D015082:2,2'-Dipyridyl; C002701:neocuproine; C018021:cobaltous chloride; D015032:Zinc; C018100:1-methylimidazole; C025205:1,10-phenanthroline