Stabilization of Diborynes versus Destabilization of Diborenes by Coordination of Lewis Bases: Unravelling the Dichotomy

Lucas de Azevedo Santos*, Daniel E. Trujillo-González, J. Oscar C. Jiménez-Halla, F. Matthias Bickelhaupt*, Miquel Solà*

*Corresponding author for this work

Research output: Contribution to JournalArticleAcademicpeer-review

Abstract

We have quantum chemically investigated the boron-boron bonds in B2, diborynes B2L2, and diborenes B2H2L2 (L=none, OH2, NH3) using dispersion-corrected relativistic density functional theory at ZORA-BLYP-D3(BJ)/TZ2P. B2 has effectively a single B−B bond provided by two half π bonds, whereas B2H2 has effectively a double B=B bond provided by two half π bonds and one σ 2p–2p bond. This different electronic structure causes B2 and B2H2 to react differently to the addition of ligands. Thus, in B2L2, electron-donating ligands shorten and strengthen the boron-boron bond whereas, in B2H2L2, they lengthen and weaken the boron-boron bond. The aforementioned variations in boron-boron bond length and strength become more pronounced as the Lewis basicity of the ligands L increases.

Original languageEnglish
Article numbere202303185
Pages (from-to)1-8
Number of pages8
JournalChemistry - A European Journal
Volume30
Issue number8
Early online date23 Oct 2023
DOIs
Publication statusPublished - Feb 2024

Bibliographical note

Publisher Copyright:
© 2023 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.

Funding

We thank the Netherlands Organization for Scientific Research (NWO) for its support. This work was carried out on the Dutch national e-infrastructure with the support of SURF Cooperative. M.S. is grateful to financial support from the Spanish Ministerio de Ciencia e Innovación (project PID2020-113711GB-I00) and the Catalan Conselleria de Recerca i Universitats of the Generalitat de Catalunya (project 2021SGR623). D.E.T.G. thanks CONACyHT for a PhD fellowship (822937). Open access funding provided by the University of Girona. We thank the Netherlands Organization for Scientific Research (NWO) for its support. This work was carried out on the Dutch national e‐infrastructure with the support of SURF Cooperative. M.S. is grateful to financial support from the Spanish Ministerio de Ciencia e Innovación (project PID2020‐113711GB‐I00) and the Catalan Conselleria de Recerca i Universitats of the Generalitat de Catalunya (project 2021SGR623). D.E.T.G. thanks CONACyHT for a PhD fellowship (822937). Open access funding provided by the University of Girona.

FundersFunder number
Catalan Conselleria de Recerca i Universitats
SURF Cooperative
Universitat de Girona, Institut d'Ecologia Aquatica
Generalitat de Catalunya822937, 2021SGR623
Nederlandse Organisatie voor Wetenschappelijk Onderzoek
Ministerio de Ciencia e InnovaciónPID2020‐113711GB‐I00

    Keywords

    • Bond theory
    • Boron
    • Density functional calculations
    • Energy decomposition analysis
    • Multiple boron-boron bonds

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