Synthesis of an o-Benzoquinone Arsenic Mononitride (As≡N) Complex and Its Reaction to Singlet Arsinonitrene

The generation and stabilization of heavier analogues of dinitrogen (N₂) remain fundamental challenges in modern inorganic and materials chemistry. In marked contrast to N₂, these species exhibit extremely high reactivities and transient lifetimes, making their synthesis, characterization, and utilization difficult. In this work, we introduce an efficient approach for the generation of an elusive o-benzoquinone─arsenic mononitride (As≡N) complex formed when ortho-phenyldioxoarsinoazide was exposed to UV or green light irradiation. Its recombination to arsinonitrene was observed upon irradiation with red light. The experimental data are well supported by density functional theory (DFT) and multireference (MS)-CASPT2(10,10)-SOC/ANO-S-VDZP electronic structure computations. DFT analyses suggest that this strategy can be extended to heavier dipnictogen systems. Our findings enhance the fundamental understanding of heavier dipnictogen chemistry and establish a versatile synthetic platform for their synthesis and subsequent practical use.