Trisubstituted geminal diazaalkene derived transient 1,2-carbodications

Mandal, Debdeep; Stein, Felix; Chandra, Sudeshna; Neuman, Nicolás I.; Sarkar, Pallavi; Das, Shubhajit; Kundu, Anupam; Sarkar, Arighna; Rawat, Hemant; Pati, Swapan K.; Chandrasekhar, Vadapalli; Sarkar, Biprajit; Jana, Anukul

doi:10.1039/d0cc02807j

Cited by 5 publications

(3 citation statements)

References 41 publications

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“…Attempts to detect the radical intermediate [ 5a ] by monitoring the reaction of 2a with [NO][SbF 6 ] / [NO 2 ][BF 4 ] at −30 °C in acetonitrile by EPR spectroscopy failed, indicating a particularly short‐lived character of this radical intermediate. [49] However, the transient formation of radical dication [ 5a ] is in accordance with the CV and DPV study of 2a (Figure S95 and Figure S97).…”

Section: Resultssupporting

confidence: 80%

Carbodicarbenes and Striking Redox Transitions of their Conjugate Acids: Influence of NHC versus CAAC as Donor Substituents

Dolai

Kumar

Elvers

et al. 2022

Chemistry A European J

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Herein, a new type of carbodicarbene (CDC) comprising two different classes of carbenes is reported; NHC and CAAC as donor substituents and compare the molecular structure and coordination to Au(I)Cl to those of NHC‐only and CAAC‐only analogues. The conjugate acids of these three CDCs exhibit notable redox properties. Their reactions with [NO][SbF6] were investigated. The reduction of the conjugate acid of CAAC‐only based CDC with KC8 results in the formation of hydrogen abstracted/eliminated products, which proceed through a neutral radical intermediate, detected by EPR spectroscopy. In contrast, the reduction of conjugate acids of NHC‐only and NHC/CAAC based CDCs led to intermolecular reductive (reversible) carbon–carbon sigma bond formation. The resulting relatively elongated carbon–carbon sigma bonds were found to be readily oxidized. They were, thus, demonstrated to be potent reducing agents, underlining their potential utility as organic electron donors and n‐dopants in organic semiconductor molecules.

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Section: Resultssupporting

confidence: 80%

Carbodicarbenes and Striking Redox Transitions of their Conjugate Acids: Influence of NHC versus CAAC as Donor Substituents

Dolai

Kumar

Elvers

et al. 2022

Chemistry A European J

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“…These unusual alkenes have also spurred interest in respective theoretical analyses of their bonding and electronic characteristics . Among them, in particular, 9,9′-bifluorenylidene VI , octahydro-4,4′-biphenanthrylidene VII , and ketene N , N ′-acetal VIII derivatives have attracted substantial attention in recent years due to their utilization as solar cell materials, in molecular machines, and in organocatalysis, respectively.…”

Section: Introductionmentioning

confidence: 99%

“…We further address the redox chemistry of the newly synthesized twisted push–pull alkenes and the formation of radical cations. Previously, radical cations from planar and twisted alkenes were reported …”

Section: Introductionmentioning

confidence: 99%

Twisted Push–Pull Alkenes Bearing Geminal Cyclicdiamino and Difluoroaryl Substituents

et al. 2021

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The systematic combination of N-heterocyclic olefins (NHOs) with fluoroarenes resulted in twisted push–pull alkenes. These alkenes carry electron-donating cyclicdiamino substituents and two electron-withdrawing fluoroaryl substituents in the geminal positions. The synthetic method can be extended to a variety of substituted push–pull alkenes by varying the NHO as well as the fluoroarenes. Solid-state molecular structures of these molecules reveal a notable elongation of the central C–C bond and a twisted geometry in the alkene motif. Absorption properties were investigated with UV–vis spectroscopy. The redox properties of the twisted push–pull alkenes were probed with electrochemistry as well as UV–vis/NIR and EPR spectroelectrochemistry, while the electronic structures were computationally evaluated and validated.

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Carbocations

Moreira

2024

Organic Reaction Mechanisms 2020

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Trisubstituted geminal diazaalkene derived transient 1,2-carbodications

Abstract: 2-Pyrrolidinyl appended trisubstituted geminal diazaalkenes were used for the synthesis of intramolecular base-stabilized dications under 2-e oxidation.

Cited by 5 publications

References 41 publications

Carbodicarbenes and Striking Redox Transitions of their Conjugate Acids: Influence of NHC versus CAAC as Donor Substituents

Carbodicarbenes and Striking Redox Transitions of their Conjugate Acids: Influence of NHC versus CAAC as Donor Substituents

Twisted Push–Pull Alkenes Bearing Geminal Cyclicdiamino and Difluoroaryl Substituents

Carbocations

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