Ligand-Based Reactivity of Oxygenation and Alkylation in Cobalt Complexes Binding with (Thiolato)phosphine Derivatives
INORGANIC CHEMISTRY(2020)
摘要
In our efforts to understand the nature of metal thiolates, we have explored the chemistry of cobalt ion supported by (thiolato)phosphine ligand derivatives. Herein, we synthesized and characterized a square-planar Co-II complex binding with a bidentate (thiolato)phosphine ligand, Co(PS1 '')(2) (1) ([PS1 '' - = [P-(Ph)(2)(C6H3-3-SiMe3-2-S)] ). The complex activates O-2 to form a ligand-based oxygenation product, Co(OPS1 '')(2) (2) ([OPS1 ''] = [PO(Ph)(2)(C6H3-3-SiMe3-2-S)](-)). In addition, an octahedral Co(III )complex with a tridentate bis(thiolato)phosphine ligand, [NEt4] [Co-(PS2*)(2)] (3) ([PS2*](2-) [P(Ph)(C6H3-3-Ph-2-S)(2-)), was obtained. Compound 3 cleaves the C-CI bond in dichloromethane via an S-based nucleophilic attack to generate a chloromethyl thioether group. Two isomeric products, [Co(PS2*)(PSSCH2Cl*)] (4 and 4') ([PSSCH2Cl*](-) = [P(Ph)(C6H3-3-Ph-2-S)(C6H3-3-Ph-2-SCH2Cl)](-)), were isolated and fully characterized. Both transformations, oxygenation of a Co-III-bound phosphine donor in 1 and alkylation of a Co m bound thiolate in 3, were monitored by spectroscopic methods. These reaction products were isolated and fully characterized. Density functional theory (DFT, the B3LYP functional) calculations were performed to understand the electronic structure of 1 as well as the pathway of its transformation to 2.
更多查看译文
关键词
cobalt complexes,oxygenation,ligand-based
AI 理解论文
溯源树
样例
![](https://originalfileserver.aminer.cn/sys/aminer/pubs/mrt_preview.jpeg)
生成溯源树,研究论文发展脉络
Chat Paper
正在生成论文摘要