Jump to main content
Jump to site search

Issue 13, 2014
Previous Article Next Article

Radical coupling for directed C–C/C–S bond formation in the reaction of Cp*IrS2C2B10H10 with 1-azido-3-nitrobenzene

Author affiliations

Abstract

Reactions of half-sandwich complex Cp*IrS2C2B10H10 (1) with 1-azido-3-nitrobenzene (3-NO2C6H4N3, L) upon heating or under light led to new complexes 2–6. Complexes 2 and 3 contain a five-membered cyclometalated ligand arising from C(sp2)–H activation of the azide ligand L. Complex 4 is a 16 electron species containing a new-generated C–C bond between the azide ligand L and the Cp* unit where C(sp3)–H activation of the methyl unit occurred. Complexes 5 and 6 contain two types of the ligand which appear in complexes 2, 3 and 4. Further reactions of complexes 5 and 6 with L under more harsh conditions gave rise to the nucleophilic addition products 7 and 8, where ring expansion of the azide ligand at the imido site of complexes 5 and 6 happened. Complexes 2–8 were characterized by NMR, MS, IR, and elemental analysis, and X-ray structural analyses were performed for complexes 2–4 and 6–8. The radical mechanisms for the formation of complexes 2–6 were proposed on the basis of capture experiments by EPR and ESI-MS. And the formation mechanism of complexes 7 and 8 was also suggested.

Graphical abstract: Radical coupling for directed C–C/C–S bond formation in the reaction of Cp*IrS2C2B10H10 with 1-azido-3-nitrobenzene

  • This article is part of the themed collection: Carboranes
Back to tab navigation

Supplementary files

Publication details

The article was received on 22 Aug 2013, accepted on 23 Sep 2013 and first published on 24 Sep 2013


Article type: Paper
DOI: 10.1039/C3DT52308J
Dalton Trans., 2014,43, 4962-4968

  •   Request permissions

    Radical coupling for directed C–C/C–S bond formation in the reaction of Cp*IrS2C2B10H10 with 1-azido-3-nitrobenzene

    W. Zhong, Q. Jiang, Q. Zhang, Y. Shang, H. Yan and V. Bregadze, Dalton Trans., 2014, 43, 4962
    DOI: 10.1039/C3DT52308J

Search articles by author

Spotlight

Advertisements