Synthesis of a stable crystalline nitrene

• 成果类型: Article
• 署名作者: Janssen, Marvin; Frederichs, Thomas; Olaru, Marian; Lork, Enno; Hupf, Emanuel; Beckmann, Jens
• 署名单位: University of Bremen; University of Bremen
• 刊物名称: SCIENCE
• ISSN/ISSBN: 0036-10578
• DOI: 10.1126/science.adp4963
• 发表日期: 2024-07-19
• 页码: 318-321
• 关键词: state perturbation-theory; singlet; carbenes; implementation; interstellar; formulation; reactivity; snapshots; chemistry; ligands

摘要

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(S)FluindN(3) (1), which gave rise to the quantitative formation of the arylnitrene M(S)FluindN (2) (M(S)Fluind 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(S)Fluind aryl substituent, electron delocalization across the central aromatic ring contributes to the electron stabilization of 2.