Preparation and Characterization of P2 BCh Ring Systems (Ch=S, Se) and Their Reactivity with N-Heterocyclic Carbenes

Cameron M E Graham; Clément R P Millet; Amy N Price; Juuso Valjus; Michael J Cowley; Heikki M Tuononen; Paul J Ragogna

doi:10.1002/chem.201704337

Preparation and Characterization of P₂ BCh Ring Systems (Ch=S, Se) and Their Reactivity with N-Heterocyclic Carbenes

Chemistry. 2018 Jan 12;24(3):672-680. doi: 10.1002/chem.201704337. Epub 2017 Dec 12.

Authors

Cameron M E Graham¹, Clément R P Millet², Amy N Price², Juuso Valjus³, Michael J Cowley², Heikki M Tuononen³, Paul J Ragogna¹

Affiliations

¹ Department of Chemistry and the Centre for Advanced Materials and Biomaterials Research, Western University, 1151 Richmond St., London, Ontario, N6A 5B7, Canada.
² EaStCHEM, School of Chemistry, University of Edinburgh, Edinburgh, EH9 3FJ, UK.
³ Department of Chemistry, Nanoscience Centre, University of Jyväskylä, P.O. Box 35, Jyväskylä, 40014, Finland.

PMID: 29119625
DOI: 10.1002/chem.201704337

Abstract

Four-membered rings with a P₂ BCh core (Ch=S, Se) have been synthesized by the reaction of phosphinidene chalcogenide (Ar*P=Ch) and phosphaborene (Mes*P=BNR₂ ). The mechanistic pathways towards these rings are explained by detailed computational work that confirmed the preference for the formation of P-P, not P-B, bonded systems, which seems counterintuitive given that both phosphorus atoms contain bulky ligands. The reactivity of the newly synthesized heterocycles, as well as that of the known (RPCh)_n rings (n=2, 3), was probed by the addition of N-heterocyclic carbenes, which revealed that all investigated compounds can act as sources of low-coordinate phosphorus species.

Keywords: N-heterocyclic carbenes; main-group heterocycles; phosphaborenes; phosphinidene chalcogenides; phosphorus.