Isolation and characterization of a triplet nitrene.

Abstract

Nitrene radical compounds are short-lived intermediates in a variety of nitrogen-involved transformations. They feature either a singlet or a triplet ground state, depending on the electronic properties of the substituents. Triplet nitrenes are highly reactive and their isolation in the condensed phase under ambient conditions is challenging. Here we report the synthesis and isolation of a triplet arylnitrene supported by a bulky hydrindacene ligand. The arylnitrene is fully characterized by various spectroscopic and structural techniques including electron paramagnetic resonance spectroscopy and single-crystal X-ray diffraction. Its high stability is largely attributed to the steric hindrance and effective electron delocalization provided by the supporting ligand. Electron paramagnetic resonance spectroscopy in conjunction with highly correlated wavefunction-based ab initio calculations provides support for a triplet ground state nitrene with axial zero-field splitting D = 0.92 cm^-1 and vanishing rhombicity E/D = 0.002.