Phosphinoborenium cations stabilized by N-heterocyclic carbenes: synthesis, structure, and reactivity

Kinga Kaniewska-Laskowska; Anna Ordyszewska; Tomasz Wojnowski; Hanna Halenka; Marcin Czapla; Jarosław Chojnacki; Rafał Grubba

doi:10.1039/d3dt03090c

Phosphinoborenium cations stabilized by N-heterocyclic carbenes: synthesis, structure, and reactivity

Dalton Trans. 2023 Nov 7;52(43):16061-16066. doi: 10.1039/d3dt03090c.

Authors

Kinga Kaniewska-Laskowska¹, Anna Ordyszewska¹, Tomasz Wojnowski¹, Hanna Halenka¹, Marcin Czapla², Jarosław Chojnacki¹, Rafał Grubba¹

Affiliations

¹ Department of Inorganic Chemistry, Faculty of Chemistry and Advanced Materials Center, Gdańsk University of Technology, Narutowicza 11/12, 80-233 Gdańsk, Poland. rafal.grubba@pg.edu.pl.
² Laboratory of Quantum Chemistry, Department of Theoretical Chemistry, Faculty of Chemistry, University of Gdańsk, Wita Stwosza 63, 80-308 Gdańsk, Poland.

PMID: 37850531
DOI: 10.1039/d3dt03090c

Abstract

Phosphinoborenium cations stabilized by N-heterocyclic carbenes (NHCs) were synthesized via the reaction of bromo(phosphino)boranes with NHCs. Their structures were investigated by heteronuclear magnetic resonance spectroscopy, X-ray diffraction, and density functional theory calculations. They possess a planar trigonal boron center directly bonded with the pyramidal phosphanyl group (PR₂) and can be treated as cationic phosphinoboranes. The reactivity of the selected NHC-phosphinoborenium cation was tested toward AuCl·SMe₂ and Ph₂PCl. In both reactions, the titled compound acted as a phosphido group donor under heterolytic cleavage of the P-B bond. Control experiments with parent phosphinoborane emphasized differences between the reactivity of low-coordinate neutral and cationic species with P-B functionality.