Photochemically and Thermally Generated BN-Doped Borafluorenate Heterocycles via Intramolecular Staudinger-Type Reactions

Bi Youan E Tra; Andrew Molino; Kimberly K Hollister; Samir Kumar Sarkar; Diane A Dickie; David J D Wilson; Robert J Gilliard Jr

doi:10.1021/acs.inorgchem.3c02284

Photochemically and Thermally Generated BN-Doped Borafluorenate Heterocycles via Intramolecular Staudinger-Type Reactions

Inorg Chem. 2023 Oct 2;62(39):15809-15818. doi: 10.1021/acs.inorgchem.3c02284. Epub 2023 Sep 16.

Authors

Bi Youan E Tra¹, Andrew Molino², Kimberly K Hollister¹, Samir Kumar Sarkar¹, Diane A Dickie³, David J D Wilson², Robert J Gilliard Jr¹

Affiliations

¹ Department of Chemistry, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Building 18-596, Cambridge, Massachusetts 02139-4307, United States.
² Department of Chemistry, La Trobe Institute for Molecular Science, La Trobe University, Melbourne, 3086, Victoria, Australia.
³ Department of Chemistry, University of Virginia, Charlottesville, Virginia 22904, United States.

PMID: 37715684
DOI: 10.1021/acs.inorgchem.3c02284

Abstract

A series of BN-incorporated borafluorenate heterocycles, bis(borafluorene-phosphinimine)s (11-15), have been formed via intramolecular Staudinger-type reactions. The reactions were promoted by light or heat using monodentate phosphine-stabilized 9-azido-9-borafluorenes (R₃P-BF-N₃; 6-10) and involve the release of dinitrogen (N₂), migration of phosphine from boron to nitrogen, and oxidation of the phosphorus center (P^III to P^V). Density functional theory (DFT) calculations provide mechanistic insight into the formation of these compounds. Compounds 11-15 are blue emissive in the solution and solid states with absolute quantum yields (Φ_F) ranging from 12 to 68%.