Department of Chemistry, Seoul National University, Seoul 151-747, South Korea.
J Am Chem Soc. 2010 Jan 13;132(1):178-84. doi: 10.1021/ja905353a.
Several zinc alkyldithiocarbamates [Zn(S(2)CNR(2))(2)] were synthesized, and their thermal decomposition in the presence of alkylamines was studied in order to understand the formation of metal sulfide nanoparticles. The major intermediates and side products were isolated under various conditions and characterized by NMR spectroscopy and LC-MS. The analysis results showed that nucleophilic attack of the metal-coordinated amine on the most electron-deficient thiocarbonyl carbon of the alkyldithiocarbamate ligands at high temperature initiated the decomposition to generate thiourea, hydrogen sulfide, and solid metal sulfide nanoparticles. From the proposed decomposition mechanism, the role of amines in thermolysis was studied, and methods for synthesizing various metal sulfide nanoparticles were generalized. Formation of the desired products was confirmed by carrying out model experiments.
合成了几种锌烷基二硫代氨基甲酸盐[Zn(S(2)CNR(2))(2)]，并研究了它们在烷基胺存在下的热分解，以了解金属硫化物纳米粒子的形成。在不同条件下分离主要中间体和副产物，并通过 NMR 光谱和 LC-MS 进行表征。分析结果表明，高温下金属配位胺对烷基金属二硫代氨基甲酸盐配体中最缺电子的硫羰基碳的亲核攻击引发了分解，生成硫脲、硫化氢和固体金属硫化物纳米粒子。从提出的分解机制中，研究了胺在热解中的作用，并概括了合成各种金属硫化物纳米粒子的方法。通过进行模型实验证实了所需产物的形成。
