Issue 37, 2024

C–H bond activation at antimony(iii): synthesis and reactivity of Sb(iii)–oxyaryl species

Abstract

We report on the synthesis, structure and reactivity of [{NCNMe4}Sb(C6H2-tBu2-3,5-O-4)] (3), an organoantimony(III)-oxyaryl species obtained upon Csp2–H bond activation in a phenolate ligand and stabilised by the monoanionic pincer {NCNMe4}. The mechanism leading to the formation of 3 is highly sensitive to steric considerations. It was probed experimentally and by DFT calculations, and a number of intermediates and related complexes were identified. All data agree with successive heterolytic bond cleaving and bond forming processes involving charged species, rather than a pathway involving free radicals as previously exemplified with congeneric bismuth species. The nucleophilic behaviour of the oxyaryl ligand in 3, a complex that features both zwitterionic and quinoidal attributes, was illustrated in derivatisation reactions. In particular, insertion of CS2 in the Sb–Coxyaryl bond generates [{NCNMe4}Sb(S2C-C6H2-tBu2-3,5-O-4)].

Graphical abstract: C–H bond activation at antimony(iii): synthesis and reactivity of Sb(iii)–oxyaryl species

Supplementary files

Article information

Article type
Paper
Submitted
13 May 2024
Accepted
30 May 2024
First published
05 Jun 2024
This article is Open Access
Creative Commons BY license

Dalton Trans., 2024,53, 15427-15440

C–H bond activation at antimony(III): synthesis and reactivity of Sb(III)–oxyaryl species

G. Duneş, M. Cordier, S. Kahlal, A. Pöllnitz, J. Saillard, C. Silvestru and Y. Sarazin, Dalton Trans., 2024, 53, 15427 DOI: 10.1039/D4DT01400F

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