| The chemistry of GroupⅡB metal thiolate complexes have received much attention as a result of their remarkable structural diversity, their applications in biological system, and as structural and functional models for active sites of some metalloproteins, metalloenzymes and bioinorganic medicines. When the N atom of N-donor-containing thiolates ligand is protonated or alkylated, it can be converted into a so-called zwitterionic ammonium thiolate carrying -NH3+, -NR2H+, or-NR3+ group, which is to some extent similar to cysteine. We are interested in a zwitterionic thiolate1 TabHPF6 (Tab = 4-(trimethylammonio)benzenethiolate) for the purpose of the preparation of new metal zwitterionic thiolate complexes. However, the reactivity of these metal complexes of the zwitterionic thiolate is less explored. In this thesis, we chose a mononucler mercury(Ⅱ)/Tab compound as a model complex to mimic the reactivity of the unsaturated HgS2 species in Hg-MerR and Hg-MT towards the naturally existed species such as inorganic anions, N-donor ligands, acids and metal ions. We also carried out the reactions of TabHPF6 with metal salts and demonstrated the reactivity of the resulting products towards other metal ions. Over 41 metal complexes of the Tab ligand were isolated and structurally characterized, which were briefly described as follows.1.Complex [Hg(Tab)2](PF6)2 (1) reacted with NaX (X = Cl, NO2, NO3) to afford mononuclear complexes [Hg(Tab)2Cl](PF6) (2), [Hg(u-Tab)(Tab)Cl]2Cl2·H2O (3·H2O), [Hg(μ-Tab) (Tab) Cl]2X2 (X = NO2 (4); NO3 (5)) and [Hg(μ-Tab)(Tab)X]2X2 (X = NO2 (6); NO3 (7)). Complexes 2-7 were confirmed by elemental analysis, IR, UV-Vis, 1H NMR, and X-ray crystallography.2.Reactions of 1 with phen, 2,2'-bipy, py, N-Meim, N-iPrim, en, eten, tmen, dap, or dpt gave rise to a family of mercury(Ⅱ) thiolate complexes, [Hg(Tab)2(L)](PF6)2·S (8: L = phen, S = 2MeOH; 9: L = 2,2'-bipy, S = DMF), [Hg(Tab)2(L)2](PF6)2 (10: L = py; 11: L = N-Meim), and [Hg(Tab)2(N-iPrim)](PF6)2 (12), [Hg(Tab)2(L)](PF6)2·0.5MeCN (13: L = en; 14: L = eten) and [Hg(Tab)2(L)](PF6)2 (15: L = tmen; 16: L = dap; 17: L = dpt). These complexes were characterized by elemental analysis, IR spectra, UV-Vis spectra, 1H NMR and single-crystal X-ray crystallography.3.Reactions of 1 with ten organic acids gave rise to a family of mercury(Ⅱ) thiolate complexes, [Hg(Tab)2(CH3COO)](PF6)·0.5H2O (18), [Hg(Tab)2(CH3CH2COO)](PF6) (19), [Hg(Tab)2(PhCOO)](PF6)H2O (20), [Hg(Tab)2(sal)](PF6)·CH3OH (21), [Hg(Tab)2(sal)](sal)·CH3OH (22), {[Hg(Tab)2]2(μ-oxa)}(PF6)2·2H2O (23), [Hg(Tab)2(OOCCH2COOH)]2(mal)·2H2O (24), {[Hg(Tab)2]2}(μ-adi)(PF6)2 (25), [Hg(Tab)2(adi)]2n (26), [Hg(Tab)2(mida)] (27). These complexes were fully characterized by elemental analysis, IR spectra, UV-Vis spectra, 1H NMR and single-crystal X-ray crystallography.4.Reactions of 1 with nicotinic acid afforded a mononuclear compound [Hg(Tab)2(nico)](PF6)·2MeCN·MeOH (28). Treatment of 28 with CdCl2 yielded one hetero- Hg/Cd cage-like cluster [Hg(Tab)2(μ-Cl)]2[Cd6Cl4(nico)12][Cd(H2O)6]·10DMF·4H2O (29) and the other Hg/Cd heteronuclear compound [Hg(Tab)2][CdCl4]·MeOH (30). The reactions of 28 with ZnCl2 only produced an anionic compound [Hg(Tab)2][ZnCl4]·MeOH (31).5.Reactions of TabHPF6 with M(OAc)2 or MCl2 gave rise to two unique adamantane-like tetranuclear complexes [M4(Tab)10](PF6)4 (M = Zn (32); Cd (33) and three mononuclear compounds [Zn(Tab)4](PF6)2·2DMF·2(H2O)0.5 (34), [Cd(Tab)4](PF6)2·3(H2O)0.5 (35) and [Hg(Tab)4] (PF6)2·2DMF (36). Treatment of 34 with MCl2 afforded three dimeric compounds [Zn2(Tab)6] (PF6)4·2DMF·2H2O (37), [Cd2(Tab)6](PF6)4·2DMF (38) and [Hg2(Tab)6](PF6)4·2DMF·2H2O (39). Reactions of ZnCl2 with TabHPF6 in the presence of N-Meim gave one mononuclear compound [Zn(Tab)2(N-Meim)2](PF6)4 (40), while these of Cd(OAc)2 with Tab afforded one dimeric compound [Cd(OAc)2(Tab)]2·2H2O (41). |
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