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- Title
1,3-Butadienyl Dianions as Non-Innocent Ligands: Synthesis and Characterization of Aromatic Dilithio Rhodacycles.
- Authors
Wei, Junnian; Zhang, Yongliang; Zhang, Wen‐Xiong; Xi, Zhenfeng
- Abstract
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 Rh3+. CDA/ECDA confirmed the electron-transfer process. 7Li 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.
- Subjects
DIANIONS; LIGANDS (Chemistry); CHEMICAL synthesis; COORDINATION compounds; AROMATIC compounds; SINGLE crystals spectra
- Publication
Angewandte Chemie International Edition, 2015, Vol 54, Issue 34, p9986
- ISSN
1433-7851
- Publication type
Article
- DOI
10.1002/anie.201504521