芳基卤化物硫醚化反应中硫醇铜（I）配合物的合成
Synthesis of Copper(I) Thiolate Complexes in the Thioetherification of Aryl Halides.
作者信息
Chen Chaohuang, Weng Zhiqiang, Hartwig John F
机构信息
Department of Chemistry, Fuzhou University, Fujian 350108, China.
出版信息
Organometallics. 2012 Nov 26;31(22):8031-8037. doi: 10.1021/om300711c. Epub 2012 Oct 4.
Abstract
The copper(I) thiophenolato complexes 1-3 containing 1,10-phenanthroline (phen) and 2,9-dimethyl-1,10-phenanthroline (Me(2)phen) were isolated in excellent yields from reactions of CuOtBu with the dative ligands and subsequent addition of 1 equiv of arylthiol and characterized spectroscopically. X-ray structural analysis of a single crystal of (phen)Cu(µ-SC(6)H(5)) (1) revealed that this complex adopts a neutral dimeric form with a weak Cu-Cu bonding interaction. These complexes were found to react with iodoarenes to form aryl sulfide products. The intermediacy of such complexes in copper-catalyzed thioetherification of aryl halides was demonstrated by the reactivity with p-tolyl iodide and o-tolyl iodide to form two aryl thioethers with selectivities similar to those of catalytic reactions conducted with the same two iodoarenes.
摘要
含1,10 - 菲咯啉（phen）和2,9 - 二甲基 - 1,10 - 菲咯啉（Me₂phen）的铜（I）苯硫酚配合物1 - 3通过[CuOtBu]₄与给体配体反应，随后加入1当量芳基硫醇，以优异的产率分离得到，并进行了光谱表征。[(phen)Cu(µ - SC₆H₅)]₂（1）单晶的X射线结构分析表明，该配合物采用具有弱Cu - Cu键相互作用的中性二聚体形式。发现这些配合物与碘代芳烃反应形成芳基硫醚产物。通过与对甲苯基碘和邻甲苯基碘反应形成两种芳基硫醚，其选择性与用相同两种碘代芳烃进行的催化反应相似，证明了此类配合物在铜催化的芳基卤化物硫醚化反应中的中间体作用。
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