Radical cations of perinaphthocyclopropanes. Conditions for the observation of 1,3-perinaphthadiyl radical cations †

Bally, Thomas; Zhu, Zhendong; Wirz, Jakob; Fülscher, Markus P.; Hasegawa, Jun‐ya

doi:10.1039/b002808h

Cited by 12 publications

(16 citation statements)

References 33 publications

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“…63 The argon-tagged 1 H -phenalene radical cation spectrum reported in this work reproduces all the features observed in the matrix spectrum within the same spectral range. This results in amendments to the previous assignments, since any features observed in the present photofragmentation spectrum must be assigned to cationic species.…”

Section: H-phenalene Radical Cation Excitation Spectrumsupporting

confidence: 70%

“…This feature was previously assigned as being carried by the neutral phenalenyl radical. 63 This is an understandable assignment. The strongest vibronic band ( ν 25 ) of the 1 2 E′′ ← X 2 A′′ 1 (D 1 ← D 0 ) transition of the phenalenyl radical had been previously observed in this region by matrix isolation spectroscopy, 64 and has been since recorded by us to have a gas-phase frequency of 19 560 cm –1 .…”

Section: H-phenalene Radical Cation Excitation Spectrummentioning

confidence: 94%

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Hydrogen-adduction to open-shell graphene fragments: spectroscopy, thermochemistry and astrochemistry

et al. 2017

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Section: H-phenalene Radical Cation Excitation Spectrumsupporting

confidence: 70%

Section: H-phenalene Radical Cation Excitation Spectrummentioning

confidence: 94%

Hydrogen-adduction to open-shell graphene fragments: spectroscopy, thermochemistry and astrochemistry

et al. 2017

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“…Unfortunately we were not able to distinguish the two isomeric forms of 13b • + by optical spectroscopy). However, if formed from the doubly bridged compound 14 the corresponding 1,3-perinaphthadiyl radical cation 15 • + is stable, and it can in turn be converted to the radical cation of the cross-conjugated polyene, 2,7-dihydro-2,2,7,7-tetramethylpyrene, 16 • + (which was generated independently from neutral 16) [18]. These results raised the question of why and how a remote methyl group can so strongly influence the tautomerization kinetics of the radical cation of methylindanone.…”

Section: Photochemistry Of Radical Cationsmentioning

confidence: 99%

“…In this way we have studied several photoinduced ring-opening reactions of radical cations containing three- [17][18][19][20][21] or four-membered rings [22][23][24][25], phototautomerizations of ionized ketones and enols [26][27][28], and rotamer inter-conversions in polyene radical cations [29][30][31]. I will use two examples to illustrate the photochemistry of radical cations:…”

Section: Photochemistry Of Radical Cationsmentioning

confidence: 99%

Photochemistry of Reactive Intermediates

Bally¹

2007

Chimia

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“…[18] The intermediates and transition states were optimized with UB3LYP/6-31 + G(d) [19] or CBS-QB3 and energies were subsequently calculated at UCCSD(T)/6-31G(d)//UB3LYP/6-31 + G(d). [20] The calculated reaction profiles for the diphenylcyclopropanes 4 and 5 are shown above (Figure 1).…”

mentioning

confidence: 99%

Electron Transfer to Benzenes by Photoactivated Neutral Organic Electron Donor Molecules

et al. 2012

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Benzene (E 0 = À3.42 V vs. a saturated calomel electrode, SCE [1] ) and its close analogs are among the most challenging organic substrates for reduction. Very few chemical entities have the power to add an electron to ground-state benzene, and these are all derived from highly reactive metals. Thus, the alkali metals sodium (E 0 = À2.71 V) and lithium (E 0 = À3.04 V) dissolve in liquid ammonia to form solvated electrons together with the corresponding metal cations, [2] and similarly calcium (E 0 = À2.89 V) and lithium dissolve in aliphatic amines.[3] These solvated electrons can convert benzene to its radical anion. In the Birch reduction, a protonation step follows for the arene radical anion, but this step is independent of the electron-rich metal. Very recently, a complex derived from samarium(II) iodide, also in the presence of an amine, joined this exclusive set of reagents, in the reduction of the substrate, 4-methoxybenzyl alcohol. [4,5] We now explore whether a completely organic molecule can convert close analogs of benzene to their radical anions, mirroring the behavior of the metals described above. The choice of arene substrate determines the level of the challenge. E 0 values are not routinely available for benzenes, [1] other than those activated by electron-withdrawing groups. However, comparison of the computed lowest unoccupied molecular orbital (LUMO) energies of a range of arenes shows [6] (see Table S1 in the Supporting Information) that benzenes substituted by saturated carbon groups have LUMO energies that lie within 0.2 eV of the value for benzene itself. In contrast, both extended arenes and arenes substituted by electron-withdrawing groups (e.g. CN, CO 2 Me) have much lower LUMO energies and are much easier to reduce. Accordingly, in choosing a discriminating test for a reducing agent, the latter substrates are not appropriate. We have chosen 1,2-diphenylcyclopropanes 4 and 5 and their derivatives 6-11 as the substrates for our study. Both 4 and 5 have LUMO energies within 0.2 eV of that of benzene, are relatively involatile, and can report the intermediacy of radical anions through the opening of the cyclopropane ring (see Scheme 1).Our recent research has probed the ground-state donor properties of highly reactive neutral organic reducing agents. Thus, we have shown that the neutral ground-state organic electron donor 1 [7,8] (Scheme 1) reduces iodoarenes [9,10] to aryl radicals [11] while the stronger donors 2[12] and 3 [13] under milder conditions, afford aryl anions from the same substrates Scheme 1. Reactions of organic electron donors with substrates.

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Radical cations of perinaphthocyclopropanes. Conditions for the observation of 1,3-perinaphthadiyl radical cations †

Cited by 12 publications

References 33 publications

Hydrogen-adduction to open-shell graphene fragments: spectroscopy, thermochemistry and astrochemistry

Hydrogen-adduction to open-shell graphene fragments: spectroscopy, thermochemistry and astrochemistry

Photochemistry of Reactive Intermediates

Electron Transfer to Benzenes by Photoactivated Neutral Organic Electron Donor Molecules

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