Carbenic nitrile imines: Properties and reactivity

Begue, Didier and Wentrup, Curt (2014) Carbenic nitrile imines: Properties and reactivity. Journal of Organic Chemistry, 79 3: 1418-1426. doi:10.1021/jo402875c

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Author Begue, Didier
Wentrup, Curt
Title Carbenic nitrile imines: Properties and reactivity
Journal name Journal of Organic Chemistry   Check publisher's open access policy
ISSN 0022-3263
1520-6904
Publication date 2014-02-07
Year available 2014
Sub-type Article (original research)
DOI 10.1021/jo402875c
Open Access Status File (Author Post-print)
Volume 79
Issue 3
Start page 1418
End page 1426
Total pages 9
Place of publication Washington, DC United States
Publisher American Chemical Society
Collection year 2015
Language eng
Subject 1605 Policy and Administration
Abstract 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 (RCNNSiMe 3 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.
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Document type: Journal Article
Sub-type: Article (original research)
Collections: Official 2015 Collection
School of Chemistry and Molecular Biosciences
 
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