Carbenic Nitrile Imines: Properties and Reactivity

• Published in: Journal of organic chemistry Vol. 79; no. 3; pp. 1418 - 1426
• Main Authors: Bégué, Didier, Wentrup, Curt
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 07.02.2014
• Subjects: Chemical Sciences
• ISSN: 0022-3263; 1520-6904
• DOI: 10.1021/jo402875c

Structures and properties of nitrile imines were investigated computationally at B3LYP and CCSD­(T) levels. Whereas NBO analysis at the B3LYP DFT level invariably predicts a propargylic electronic structure, CCSD­(T) calculations permit a clear distinction between propargylic, allenic, and carbenic structures. Nitrile imines with strong IR absorptions above ca. 2150 cm–1 have propargylic structures with a CN triple bond (RCNNSiMe3 and R2BCNNBR2), and those with IR absorptions below ca. 2150 cm–1 are allenic (HCNNH, PhCNNH, and HCNNPh). Nitrile imines lacking significant cumulenic IR absorptions at 1900–2200 cm–1 are carbenic (R–(C:)–NN–R′). Electronegative but lone pair-donating groups NR2, OR, and F stabilize the carbenic form of nitrile imines in the same way they stabilize “normal” singlet carbenes, including N-heterocyclic carbenes. NBO analyses at the CCSD­(T) level confirm the classification into propargylic, allenic, and carbenic reactivity types. Carbenic nitrile imines are predicted to form azoketenes 21 with CO, to form [2+2] and [2+4] cycloadducts and borane adducts, and to cyclize to 1H-diazirenes of the type 24 in mildly exothermic reactions with activation energies in the range 29–38 kcal/mol. Such reactions will be readily accessible photochemically and thermally, e.g., under the conditions of matrix photolysis and flash vacuum thermolysis.