A. �X. Zheng, J. Shi, X. �Y. Tang, L. �L. Miao, M. Yu, K. �P. Hou, F. Wang, H. �X. Li, J. �P. Lang*, Reactions of the Cationic Zinc Thiolate Model Complex [Zn(Tab)4](PF6)2 with N-Donor Ligands and Cobalt Dichloride, Inorg. Chem., 2012, 51, 10262-10273.Treatment of [Zn(Tab)4](PF6)2 (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(pyrazd-3-yl)pyridine (bppy) or with CoCl2・6H2O 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 Zn(II) or Co(III)/Co(II) thiolate complexes, [Zn(Tab)2(L)](PF6)2 (2: L = 2,2′-bipy, 3: L = phen, 4: L = 2,9-dmphen), [Zn(Tab)2(N-Meim)2](PF6)2 (5), [Zn(Tab)2(bppy)](PF6)2 (6), [Co(Tab)2(L)2](PF6)3 (7: L = 2,2′-bipy, 8: L = phen, 9: L = 4,4′-dmbpy), and [Co(Tab)(bdmppy)Cl](PF6) (10). These compounds were characterized by elemental analysis, IR spectra, UV-Vis spectra, 1H NMR, electrospray ionization mass spectra and single-crystal X-ray diffraction.