A Phosphine‐Coordinated Boron‐Centered Gomberg‐Type Radical1. (26th June 2015)

• Record Type: Journal Article
• Authors: Rosenthal, Amos J.; Devillard, Marc; Miqueu, Karinne; Bouhadir, Ghenwa; Bourissou, Didier
• Is Part Of: Angewandte Chemie. Volume 127:Number 32(2015)
• Page Start: 9330
• Page End: 9334
• Publication Date: 2015-06-26
• Subjects: Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.201504502
• Languages: English
• ISSNs: 0044-8249

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>The P‐coordinated boryl radical [Ph₂P(naphthyl)BMes]^. (Mes=mesityl) was prepared by (electro)chemical reduction of the corresponding borenium salt or bromoborane. Electron paramagnetic resonance (EPR) analysis in solution and DFT calculations indicate large spin density on boron (60–70 %) and strong P–B interactions (P→B σ donation and B→P negative hyperconjugation). The radical is persistent in solution and participates in a Gomberg‐type dimerization process. The associated quinoid‐type dimer has been characterized by single‐crystal X‐ray diffraction.</p> </abstract>