Mechanistic insight into the N=N bond-cleavage of Azo-compounds that was induced by an Al-Al-bonded compound [L 2-Al II-Al IIL 2-]

Yanxia Zhao, Yanyan Liu, Ling Yang, Jian Guo Yu, Shaoguang Li, Biao Wu, Xiao Juan Yang*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

65 Citations (Scopus)

Abstract

An α-diimine-stabilized Al-Al-bonded compound [L 2-Al II-Al IIL 2-] (L=[{(2,6-iPr 2C 6H 3)NC(Me)} 2]; 1) consists of dianionic α-diimine ligands and sub-valent Al 2+ ions and thus could potentially behave as a multielectron reductant. The reactions of compound 1 with azo-compounds afforded phenylimido-bridged products [L -Al III2-NPh)(μ 2-NAr)Al IIIL -] (2-4). During the reaction, the dianionic ligands and Al 2+ ions were oxidized into monoanions and Al 3+, respectively, whilst the [NAr] 2- imides were produced by the four-electron reductive cleavage of the N=N double bond. Upon further reduction by Na, the monoanionic ligands in compound 2 were reduced to the dianion to give [(L 2-) 2Al III 22-NPh) 2Na 2(thf) 4] (5). Interestingly, when asymmetric azo-compounds were used, the asymmetric adducts were isolated as the only products (compounds 3 and 4). DFT calculations indicated that the reaction was quite feasible in the singlet electronic state, but the final product with the triplet-state monoanionic ligands could result from an exothermic singlet-to-triplet conversion during the reaction process.

Original languageEnglish
Pages (from-to)6022-6030
Number of pages9
JournalChemistry - A European Journal
Volume18
Issue number19
DOIs
Publication statusPublished - 7 May 2012
Externally publishedYes

Keywords

  • aluminum
  • azo compounds
  • cleavage reactions
  • reaction mechanisms
  • reduction

Fingerprint

Dive into the research topics of 'Mechanistic insight into the N=N bond-cleavage of Azo-compounds that was induced by an Al-Al-bonded compound [L 2-Al II-Al IIL 2-]'. Together they form a unique fingerprint.

Cite this