Magnetically Bistable Nitrenes: Matrix Isolation of Furoylnitrenes in Both Singlet and Triplet States and Triplet 3-Furylnitrene

Ruijuan Feng^†,Yan Lu^†,Guohai Deng^†,Jian Xu^†,Zhuang Wu^†,Hongmin Li^†,Qian Liu^†,Norito Kadowaki^‡,Manabu Abe^‡, andXiaoqing Zeng^*†（曾小庆）

^†College of Chemistry, Chemical Engineering and Materials Science,Soochow University, Suzhou 215123,China

^‡Department of Chemistry, Graduate School of Science,Hiroshima University, 1-3-1 Kagamiyama, Higashi-Hiroshima, Hiroshima 739-8526,Japan

J. Am. Chem. Soc.,2018,140(1), 10--13

Two simple acylnitrenes, 2-furoylnitrene (2) and 3-furoylnitrene (6), were generated through 266 nm laser photolysis of the corresponding azides. Both are magnetically bistable in cryogenic matrices, as evidenced by the direct observation of the closed-shell singlet state with IR spectroscopy in solid Ne, Ar, Kr, Xe, and N₂matrices (3–40 K) and the triplet state in toluene (10 K) with EPR spectroscopy (³2: |D/hc| = 1.48 cm^–1and |E/hc| = 0.029 cm^–1;³6: |D/hc| = 1.39 cm^–1and |E/hc|c= 0.039 cm^–1). Subsequent visible-light and UV laser irradiations led to the formation of furyl isocyanates (3and7) and ring-opening product 3-cyanoacrolein (9-Eand9-Z), respectively, in which the elusive 3-furylnitrene (³8) was also identified by IR and EPR spectroscopy (|D/hc| = 1.12 cm^–1and |E/hc| = 0.005 cm^–1).

链接：https://pubs.acs.org/doi/10.1021/jacs.7b08957