Synthesis of a stable crystalline nitrene

Abstract

Nitrenes are a highly reactive, yet fundamental, compound class. They possess a monovalent nitrogen atom and usually a short life span, typically in the nanosecond range. Here, we report on the synthesis of a stable nitrene by photolysis of the arylazide M^SFluindN₃ (1), which gave rise to the quantitative formation of the arylnitrene M^SFluindN (2) (M^SFluind is dispiro[fluorene-9,3'-(1',1',7',7'-tetramethyl-s-hydrindacen-4'-yl)-5',9''-fluorene]) that remains unchanged for at least 3 days when stored under argon atmosphere at room temperature. The extraordinary life span permitted the full characterization of 2 by single-crystal x-ray crystallography, electron paramagnetic resonance spectroscopy, and superconducting quantum interference device magnetometry, which supported a triplet ground state. Theoretical simulations suggest that in addition to the kinetic stabilization conferred by the bulky M^SFluind aryl substituent, electron delocalization across the central aromatic ring contributes to the electron stabilization of 2.