Generation of<i>N</i>,<i>N</i>-Di(4-bromophenyl)nitrenium Ion under Acidic Conditions: Search for a Nitrenium Dication

Zeppuhar, Andrea N.; Falvey, Daniel E.

doi:10.1021/acs.joc.0c00686

Cited by 4 publications

(1 citation statement)

References 34 publications

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“…Similar nitrenium ions have been made through oxidation of the corresponding amines and/or through photolysis of N-aminopyridinium ions. [29][30][31] It is proposed that 3 and/or 5 (or substituted derivatives) can be formed by generation of 9 in the presence of acetylene. Specific effects of counterions, solvents, leaving groups and other reagents remain to be examined.…”

Section: N Hmentioning

confidence: 99%

Azapyramidinium Ion and iso-Azapyramidinium Ion: Mechanisms for their Synthesis, Interconversion, and Decomposition

Falvey

2023

Preprint

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The properties and reactivity of azapyramidinium ion 3 were examined using coupled-cluster theory and density functional theory with the goal of identifying synthetic routes and anticipating decay pathways. It is shown that azapyramidinium ion is nearly isoenergetic with an isomer that results from transposition of the apical nitrogen atom with a basal CH group. The latter is termed the “iso-azapyramidinium ion” 5. There is a low energy kinetic barrier (ca. 14 kcal/mol) connecting the two isomers, suggesting they would interconvert rapidly at ambient temperatures. The two isomers show substantial barriers for both isomerization to the lower energy pyrrolenium ion as well as elimination of HCN to form the cyclopropenium ion. Thus 3 and 5 should be isolable (if as an equilibrium mixture) if segregated from reactive partners. Water is shown to react rapidly with the azapyramidinium isomers. Finally, analysis of the potential energy surface for (CH)¬4N+ shows that 5 and/or 3 should be accessible through addition of acetylene to the azirenium ion. Proposed synthetic routes are discussed.

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Section: N Hmentioning

confidence: 99%

Azapyramidinium Ion and iso-Azapyramidinium Ion: Mechanisms for their Synthesis, Interconversion, and Decomposition

Falvey

2023

Preprint

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Radical Reactions

Parsons,

Parsons

2024

Organic Reaction Mechanisms 2020

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Photochemical generation and characterization of the 5-endo-10,11-dihydrodibenzoazepine nitrenium ion

Chinn

Falvey

2022

Photochem Photobiol Sci

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A photochemical precursor to the 5-endo-10,11-dihydroazepine nitrenium ion (1) was synthesized and used to characterize the intermediate by laser flash photolysis and stable product analysis. In addition, DFT calculations were carried out on the nitrenium ion. These results were compared with earlier studies on the diphenylnitrenium ion in order to ascertain the effect of the 2 carbon bridge on the reactions and properties of 1. It is shown that the geometric constraints provided by the bridging group (a) destabilize the triplet state of 1 relative to the singlet state (b) substantially increase the lifetime of 1 relative to Ph 2 N + by inhibiting the unimolecular cyclization pathway possible in the latter and (c) modestly increases the barrier for nucleophilic addition to the ring carbons.

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Generation ofN,N-Di(4-bromophenyl)nitrenium Ion under Acidic Conditions: Search for a Nitrenium Dication

Cited by 4 publications

References 34 publications

Azapyramidinium Ion and iso-Azapyramidinium Ion: Mechanisms for their Synthesis, Interconversion, and Decomposition

Azapyramidinium Ion and iso-Azapyramidinium Ion: Mechanisms for their Synthesis, Interconversion, and Decomposition

Radical Reactions

Photochemical generation and characterization of the 5-endo-10,11-dihydrodibenzoazepine nitrenium ion

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