The electronic structure of nitrilimine: absence of the carbenic form

Cargnoni, Fausto; Molteni, Giorgio; Raimondi, Mario; Ponti, Alessandro

doi:10.1039/b517030c

Cited by 22 publications

(15 citation statements)

References 18 publications

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“…However, Ponti and co-workers have used CASSCF and spin-coupled calculations to show that the most important electronic structure of nitrilimines corresponds to the propargylic resonance form with little or no carbenic character. [71] …”

Section: Configuration Mixing Modelsmentioning

confidence: 97%

Conceptual, Qualitative, and Quantitative Theories of 1,3‐Dipolar and Diels–Alder Cycloadditions Used in Synthesis

2006

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Abstract:The application and performance of conceptual and qualitative theories and quantitative quantum mechanical methods to the study of mechanism, reactivity, and selectivity of 1,3-dipolar and Diels-Alder cycloadditions are reviewed. This review emphasizes the application of conceptual density functional theory (DFT) for predicting reactivity and regioselectivity, and highly accurate quantum mechanical methods for predicting barrier heights and reaction energetics. Applications of computations to solvation effects, metal and organocatalysis, are also described.

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Section: Configuration Mixing Modelsmentioning

confidence: 97%

Conceptual, Qualitative, and Quantitative Theories of 1,3‐Dipolar and Diels–Alder Cycloadditions Used in Synthesis

2006

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“…[20] Different ways to describe the geometric and electronic structures of the parent nitrile imine have also been reported by means of valence bond (VB) calculations. [13,21] Scheme 1. Different resonance forms that can represent the structure of a nitrile imine.…”

Section: Introductionmentioning

confidence: 99%

The Quest for Carbenic Nitrile Imines: Experimental and Computational Characterization of C‐Amino Nitrile Imine

et al. 2015

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C‐Amino nitrile imine has been generated as primary photoproduct (λ = 220 nm) of 5‐amino‐2H‐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 1H‐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.

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“…More recent DFT calculations in combination with the natural resonance theory indicated that all four resonance structures are necessary for a full description and that the carbenic form dominates for F-CNN-F and H 2 N-CNN-NH 2 8. In contrast, a spin-coupled valence bond calculation using the geometry from a CASSCF calculation suggested that the stable electronic structure of H-CNN-H is predominantly propargylic 9. To provide direct evidence, herein we report the use of photocrystallography10 to observe for the first time the structure of a non-stabilized nitrile imine generated photochemically in situ in the solid state.…”

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confidence: 99%

Direct Observation of a Photoinduced Nonstabilized Nitrile Imine Structure in the Solid State

Zheng

Wang

et al. 2009

J. Am. Chem. Soc.

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We report the direct observation of a bent geometry for a non-stabilized nitrile imine in a metal-coordination crystal. The photoinduced tetrazole ring rupture to release N2 appears to depend on the size of voids around the N3-N4 bond in the crystal lattice. We further observed the selective formation of 1,3-addition product when a reactive nitrile imine was photo-generated in water. Taken together, the bent nitrile imine geometry agrees with the 1,3-dipolar structure, a transient reactive species that mediates the photoinduced 1,3-dipolar cycloaddition in the aqueous medium.

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The electronic structure of nitrilimine: absence of the carbenic form

Abstract: The electronic structure of nitrilimine HCNNH is shown to essentially be propargylic by CASSCF and Spin-Coupled (modern VB) calculations; in contrast to a recent claim, the carbenic resonance form is absent.

Cited by 22 publications

References 18 publications

Conceptual, Qualitative, and Quantitative Theories of 1,3‐Dipolar and Diels–Alder Cycloadditions Used in Synthesis

Conceptual, Qualitative, and Quantitative Theories of 1,3‐Dipolar and Diels–Alder Cycloadditions Used in Synthesis

The Quest for Carbenic Nitrile Imines: Experimental and Computational Characterization of C‐Amino Nitrile Imine

Direct Observation of a Photoinduced Nonstabilized Nitrile Imine Structure in the Solid State

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