Beijing National Laboratory for Molecular Sciences (BNLMS), Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, College of Chemistry, Peking University, Beijing 100871 (China).
Angew Chem Int Ed Engl. 2015 Aug 17;54(34):9986-90. doi: 10.1002/anie.201504521. Epub 2015 Jul 1.
Herein we report that 1,4-dilithio-1,3-butadienes, a type of 1,3-butadienyl dianion, can act as non-innocent ligands, taking electrons from low-valent transition metals. Dilithio reagents reacted with [{RhCl(cod)}2] to give dilithio rhodacycle 3 a. Single-crystal X-ray structural analysis revealed the structure of 3 a with averaged bond lengths. XPS data suggested that the oxidation state of Rh in 3 a was more likely to be Rh(3+). CDA/ECDA confirmed the electron-transfer process. (7)Li NMR spectra of 3 a and theoretical calculations revealed a considerable aromatic character. In this process, the dilithio compounds behaved as non-innocent ligands and formal oxidants. These results demonstrated that organolithium compounds with suitable π-conjugation could be used as electron acceptor.
在此，我们报告 1,4-二锂-1,3-丁二烯，一种 1,3-丁二烯二负离子，可作为非配位性配体，从低价过渡金属中获取电子。二锂试剂与[{RhCl(cod)}2]反应生成二锂铑环 3a。单晶 X 射线结构分析揭示了 3a 的平均键长结构。XPS 数据表明 3a 中 Rh 的氧化态更可能是 Rh(3+)。CDA/ECDA 证实了电子转移过程。3a 的 (7)Li NMR 谱和理论计算表明其具有相当大的芳香性。在这个过程中，二锂化合物表现出非配位性配体和形式氧化剂的性质。这些结果表明，具有合适π共轭体系的有机锂化合物可用作电子受体。
