The Quest for Carbenic Nitrile Imines: Experimental and Computational Characterization of C‐Amino Nitrile Imine. Issue 34 (22nd October 2015)

• Record Type: Journal Article
• Authors: Nunes, Cláudio M.; Reva, Igor; Rosado, Mário T. S.; Fausto, Rui
• Is Part Of: European journal of organic chemistry. Issue 34(2015)
• Page Start: 7484
• Page End: 7493
• Publication Date: 2015-10-22
• Subjects: Nitrile imines -- Structure elucidation -- Matrix isolation -- Photochemistry -- Density functional calculations; Chemistry, Organic -- Periodicals; Organic compounds -- Synthesis -- Periodicals; Bioorganic chemistry -- Periodicals; Chemistry, Physical organic -- Periodicals; 547
• DOI: 10.1002/ejoc.201501153
• Languages: English
• ISSNs: 1434-193X

Abstract

Abstract: C ‐Amino nitrile imine has been generated as primary photoproduct ( λ = 220 nm) of 5‐amino‐2 H ‐tetrazole isolated in an argon matrix at 15 K. Subsequent photochemical experiments ( λ = 330 nm) demonstrated that C ‐amino nitrile imine isomerizes to the corresponding three‐membered‐ring 1 H ‐diazirine and decomposes to methylenimine. The experimentally observed νas (CNN) absorption at 1998 cm –1 and a carbenic resonance structure contribution of around 20 %, predicted by natural resonance theory calculations, demonstrate that the protoproduced C ‐amino nitrile imine has significant carbenic character. These results pave the way to the discovery of carbenic nitrile imines. Abstract : C ‐Amino nitrile imine has been generated in a low‐temperature matrix. Experimental and computational characterization has demonstrated that C ‐amino nitrile imine has significant carbenic character. These results pave the way to the discovery of carbenic nitrile imines.