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Dianions as Formal Oxidants: Synthesis and Characterization of Aromatic Dilithionickeloles from 1,4‐Dilithio‐1,3‐butadienes and [Ni(cod) 2 ]
Author(s) -
Wei Junnian,
Zhang WenXiong,
Xi Zhenfeng
Publication year - 2015
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201411009
Subject(s) - oxidizing agent , redox , chemistry , oxidation state , x ray photoelectron spectroscopy , characterization (materials science) , crystal structure , polymer chemistry , medicinal chemistry , photochemistry , inorganic chemistry , crystallography , organic chemistry , materials science , catalysis , nanotechnology , chemical engineering , engineering
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 Ni 2+ . 7 Li 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 Ni 0 into Ni 2+ . These results demonstrated that organolithium compounds with π‐conjugation could be used as oxidants and could continue to accept extra electrons.