Dianions as Formal Oxidants: Synthesis and Characterization of Aromatic Dilithionickeloles from 1,4‐Dilithio‐1,3‐butadienes and [Ni(cod)2] |
| |
| Authors: | Junnian Wei Prof. Dr. Wen‐Xiong Zhang Prof. Dr. Zhenfeng Xi |
| |
| Affiliation: | 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) |
| |
| Abstract: | Organolithium compounds can behave as reductants but never as oxidants in redox reactions. Reported herein is that 1,4‐dilithio‐1,3‐butadienes reacted with [Ni(cod)2] (cod=1,5‐cyclooctadiene) to deliver dilithionickeloles. Single‐crystal X‐ray structural analysis revealed a coplanar structure of dilithionickeloles with an averaging of bond lengths. XPS data confirmed the oxidation state of Ni in dilithionickeloles was Ni2+. 7Li NMR spectra of dilithionickeloles and theoretical calculations revealed a considerable aromatic character. In this redox reaction, the dilithio dianionic compounds behaved as formal oxidants, thus oxidizing Ni0 into Ni2+. These results demonstrated that organolithium compounds with π‐conjugation could be used as oxidants and could continue to accept extra electrons. |
| |
| Keywords: | aromaticity lithium nickel oxidation redox chemistry |
|
|
