1, 3‐Butadienyl Dianions as Non‐Innocent Ligands: Synthesis and Characterization of Aromatic Dilithio Rhodacycles. Issue 34 (1st July 2015)

• Record Type: Journal Article
• Authors: Wei, Junnian; Zhang, Yongliang; Zhang, Wen‐Xiong; Xi, Zhenfeng
• Is Part Of: Angewandte Chemie international edition. Volume 54:Issue 34(2015)
• Page Start: 9986
• Page End: 9990
• Publication Date: 2015-07-01
• Subjects: dianions -- lithium -- metallacycles -- redox reaction -- rhodium; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201504521
• Languages: English
• ISSNs: 1433-7851

Abstract

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 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. Abstract : Give and take : Dilithio reagents that are a type of 1, 3‐butadienyl dianion react with [{RhCl(cod)}2 ] to give aromatic dilithio rhodacycles. In this process, the dilithio compounds behave as non‐innocent ligands and formal oxidants. Thus organolithium compounds with suitable π conjugation can act as electron acceptors.