Two‐Orbital Three‐Electron Stabilizing Interaction for Direct Co2+As3+ Bonds involving Square‐Planar CoO4 in BaCoAs2O51. (12th February 2014)

• Record Type: Journal Article
• Authors: David, Rénald; Kabbour, Houria; Pautrat, Alain; Touati, Nadia; Whangbo, Myung‐Hwan; Mentré, Olivier
• Is Part Of: Angewandte Chemie. Volume 126:Number 12(2014)
• Page Start: 3175
• Page End: 3178
• Publication Date: 2014-02-12
• Subjects: Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.201311183
• Languages: English
• ISSNs: 0044-8249

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>The quest for new oxides with cations containing active lone‐pair electrons (<italic>E</italic>) covers a broad field of targeted specificities owing to asymmetric electronic distribution and their particular band structure. Herein, we show that the novel compound BaCoAs₂O₅, with lone‐pair As³⁺ ions, is built from rare square‐planar Co²⁺O₄ involved in direct bonding between As³⁺<italic>E</italic> and Co²⁺ d_{<italic>z</italic>2} orbitals (CoAs=2.51 Å). By means of DFT and Hückel calculations, we show that this σ‐type overlapping is stabilized by a two‐orbital three‐electron interaction allowed by the high‐spin character of the Co²⁺ ions. The negligible experimental spin‐orbit coupling is expected from the resulting molecular orbital scheme in O₃As<italic>E</italic>–CoO₄ clusters.</p> </abstract>