Browse by author
Lookup NU author(s): Professor William Clegg
This work is licensed under a Creative Commons Attribution 4.0 International License (CC BY 4.0).
Protonation of the macropolyhedral chalcogenaborane anions [E2B17H18]⁻ (E = S, 1a⁻; Se, 1b⁻) induces a radical cluster rearrangement, yielding the new metastable isoelectronic neutral species E2B17H19 (2a and 2b). This transformation converts the original structure comprising two identical ‘arachno’ ten-vertex subclusters into a new architecture with two distinct ‘nido’ ten-vertex subclusters. Notably, one of the chalcogen atoms, which originally was a tri-connected cluster vertex in anions 1⁻, is extruded, forming a bridging μ₂-{EH} unit. Remarkably, deprotonation of compounds 2 facilitates a boronotropic dehydrogenation, giving reintegration of the extruded {EH} unit and regeneration of the original [E2B17H18]⁻ anions 1⁻. Compound 2a is characterized by a single-crystal X-ray diffraction study, and by agreement between experimental and DFT-calculated multielement NMR spectra. Also, for 2b, the measured and calculated d(⁷⁷Se) values for the two widely separated selenium resonances add further support. Metastable compounds 2 ultimately eliminate dihydrogen to yield the known neutral E2B17H17 compounds 3. For 2b, a competing pathway leads to loss of selenium, to give known SeB17H19 4.
Author(s): Bould J, Litecká M, Clegg W, Ehn M, Kennedy JD, Londesborough MGS
Publication type: Article
Publication status: Published
Journal: Inorganic Chemistry
Year: 2026
Volume: 65
Issue: 8
Pages: 4382-4389
Print publication date: 02/03/2026
Online publication date: 18/02/2026
Acceptance date: 05/02/2026
Date deposited: 07/02/2026
ISSN (print): 0020-1669
ISSN (electronic): 1520-510X
Publisher: American Chemical Society
URL: https://doi.org/10.1021/acs.inorgchem.5c03815
DOI: 10.1021/acs.inorgchem.5c03815
Data Access Statement: Deposition Number 2452393 contains the supporting crystallographic data for this paper. These data can be obtained free of charge via the joint Cambridge Crystallographic Data Centre (CCDC) and Fachinformationszentrum Karlsruhe Access Structures service.
Altmetrics provided by Altmetric
