Synthesis And The Research Of Its Complexes With Transition Metal Of A New Style Of Thiophenol Ligands

The series of p-amino-benzenethiol compounds play key roles in synthetic chemistry and inorganic coordination chemistry. In synthetic chemistry, by using p-Amino-benzenethiol compounds, some further structure such as thioethers, asymmetric or symmetric disulfides, sulfoxides or sulfones could be obtained. In coordination chemistry, these compounds are usually used as important ligands to react with various metals, such as transition metal and rare earth metal. Traditionally, strong acid or basic conditions were always involved in the preparation of the ligands mentioned above. In this thesis, we firstly synthesized a few nitrogen-containing aromatic thiols under weak acidic conditions and acquired their derivatives. Then these ligands were used to study the reaction with metal.1: Mild three-step synthesis route gives rise to the p-amino-benzenethiol compounds. The roution contains: 1) The nucleophilic substitution reaction of N atom. 2) The thiocyanation of the para position of phenyl group. BDMS(bromodimethylsulfonium bromide)/NH4SCN was chosen as a suitable system to gain the aimed products efficiently. 3) Zn/HOAc system reduces the oxidation products above to the benzenethiols without changing the active functional group like -COOEt, -CN. Four products containing different functional group, involving -COOEt, -CN, -CH(CH3)Ph and -CH2CH=CH2, were obtained through this roution with the yields from 73% to 87%.2: Synthesizing the derivatives of p-amino-benzenethiol compounds. Disulfides could be gained via S2Cl2 or by converting the aromatic thiocyanate compounds under basic condition. Acylating the p-amino-benzenethiol compounds lead to the S-substituted-esters. Two kinds of chiral-N-containing quaternar ammonium salts were made by using CF3SO3CH3 in the methylation reaction with S-substituted-esters. All the products were identified by N-HMR and MS.3: Synthesizing the coordination compounds. Using benzenethiol ligand (3c) to react with Pb(OAc)2 resulted in a unique 1D spiral Pb-S chain product. Reaction of the zwitterionic thiolate Tab(Tab = 4-(trimethylammonio)benzenethiolate) with Hg(OAc)2 afforded compound [Hg(Tab)2](PF6)2, which was used to react with ebbm or hbbm (2:1) and corresponding [Hg(Tab)2(ebbm)](PF6)2(II) and {[Hg(Tab)2]2(μ-hbbm)}(PF6)4(Ш) were obtained. Due to the existence of H-bonds, both compounds (II) and (Ш) displayed 3-D framework.