Isolation, bonding and reactivity of a monomeric stibine oxide

Autor: John S. Wenger, Monica Weng, Graham N. George, Timothy C. Johnstone
Rok vydání: 2023
Předmět:
Zdroj: Nature Chemistry. 15:633-640
ISSN: 1755-4349
1755-4330
DOI: 10.1038/s41557-023-01160-x
Popis: In contrast to phosphine oxides and arsine oxides, which are common and exist as stable monomeric species featuring the corresponding pnictoryl functional group (Pn=O/Pn+–O−; Pn = P, As), stibine oxides are generally polymeric, and the properties of the unperturbed stiboryl group (Sb=O/Sb+–O−) remain unexplored. We now report the isolation of the monomeric stibine oxide, Dipp3SbO (where Dipp = 2,6-diisopropylphenyl). Spectroscopic, crystallographic and computational studies provide insight into the nature of the Sb=O/Sb+–O− bond. Moreover, isolation of Dipp3SbO allows the chemistry of the stiboryl group to be explored. Here we show that Dipp3SbO can act as a Brønsted base, a hydrogen-bond acceptor and a transition-metal ligand, in addition engaging in 1,2-addition, O-for-F2 exchange and O-atom transfer. In all cases, the reactivity of Dipp3SbO differed from that of the lighter congeners Dipp3AsO and Dipp3PO.
Databáze: OpenAIRE
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