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1,3‐Butadienyl Dianions as Non‐Innocent Ligands: Synthesis and Characterization of Aromatic Dilithio Rhodacycles
Author(s) -
Wei Junnian,
Zhang Yongliang,
Zhang WenXiong,
Xi Zhenfeng
Publication year - 2015
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201504521
Subject(s) - chemistry , x ray photoelectron spectroscopy , oxidation state , electron acceptor , reagent , transition metal , acceptor , medicinal chemistry , photochemistry , crystallography , organic chemistry , catalysis , physics , condensed matter physics , nuclear magnetic resonance
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.