Isolation, bonding and reactivity of a monomeric stibine oxide

Wenger, John S.; Weng, Monica; George, Graham N.; Johnstone, Timothy C.

doi:10.1038/s41557-023-01160-x

Title: Isolation, bonding and reactivity of a monomeric stibine oxide

Journal Article · 23 March 2023 · Nature Chemistry

DOI: https://doi.org/10.1038/s41557-023-01160-x · OSTI ID:1963111

; Weng, Monica;

;

Abstract 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, Dipp ₃ SbO (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 Dipp ₃ SbO allows the chemistry of the stiboryl group to be explored. Here we show that Dipp ₃ SbO can act as a Brønsted base, a hydrogen-bond acceptor and a transition-metal ligand, in addition engaging in 1,2-addition, O-for-F ₂ exchange and O-atom transfer. In all cases, the reactivity of Dipp ₃ SbO differed from that of the lighter congeners Dipp ₃ AsO and Dipp ₃ PO.

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Sponsoring Organization:: USDOE

Grant/Contract Number:: AC02-76SF00515

OSTI ID:: 1963111

Journal Information:: Nature Chemistry, Journal Name: Nature Chemistry Journal Issue: 5 Vol. 15; ISSN 1755-4330

Publisher:: Nature Publishing GroupCopyright Statement

Country of Publication:: United Kingdom

Language:: English

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