Synthesis and Properties of Chalcogen‐bridged Naphthalenes: A New Series of Electron Donors*

Dauplaise, David; Meinwald, Jerrold; Scott, J. C.; Temkin, H.; Clardy, Jon

doi:10.1111/j.1749-6632.1978.tb39433.x

Cited by 26 publications

(1 citation statement)

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“…The naphthalene 1,8- peri -dichalcogenides 1a , , 1b and 1c (Chart ) have been known for many years and are easily synthesized from 1,8-dibromonaphthalene via transmetalation with n -butyllithium, followed by treatment with elemental sulfur, selenium, or tellurium . These and closely related compounds have been studied extensively in several contexts, including their use as electron donors in charge transfer complexes and organic conductors . The ability of 1a and 1b and their derivatives to form complexes with various metals and metalloids via the corresponding dithiols and diselenols has been extensively studied by the groups of Woollins, − Tilley, and Grainger .…”

Section: Introductionmentioning

confidence: 99%

Acid-Catalyzed Electron Transfer Processes in Naphthalene peri-Dichalcogenides

et al. 2018

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1,8-Naphthalene peri-dichalcogenides undergo protonation by Bronsted acids to produce electrophilic cations. Single electron transfer (SET) from the remaining unprotonated electron-rich peri-dichalcogenide to the cation then generates a radical cation and a radical. Thus, the formation of radical species results in severe peak broadening and coalescence of NMR signals when trifluoroacetic acid or other strong acids are added to the peri-dichalcogenide, and the process can be reversed by treatment with base. Further evidence for the formation of radicals stems from EPR, radical quencing with sodium dithionite, and computational experiments. The electron transfer is enhanced by the presence of 2,7-dialkoxy substituents that further increase the electron-donating ability of the dichalcogenides. This is an unusual example of a proton-coupled electron transfer process where an electron-rich molecule reacts with its own conjugate acid via a single electron transfer process.

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Section: Introductionmentioning

confidence: 99%

Acid-Catalyzed Electron Transfer Processes in Naphthalene peri-Dichalcogenides

et al. 2018

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Tellurium‐Containing Heterocycles as Donor Molecules

1994

Chemistry of Heterocyclic Compounds: A Series of Monographs

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Torsional Angular Dependence of ¹J(Se,Se) and Fermi Contact Control of ⁴J(Se,Se): Analysis of ⁿJ(Se,Se) (n=1–4) Based on Molecular Orbital Theory

Nakanishi

Hayashi

2008

Chemistry A European J

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(n)J(Se,Se) (n=1-4) nuclear couplings between Se atoms were analyzed by using molecular orbital (MO) theory as the first step to investigating the nature of bonded and nonbonded (n)J(Se,Se) interactions between Se atoms. The values were calculated by employing Slater-type triple xi basis sets at the DFT level, which were applied to structures optimized with the Gaussian 03 program. The contribution from each occupied MO (psi(i)) and psi(i)-->psi(a) (psi(a)=unoccupied MO) transition was evaluated separately. 1J(Se,Se) was calculated for the MeSeSeMe model compound, which showed a typical dependence on the torsion angle (phi(C(Me)SeSeC(Me))). This dependence explains the small values (< or =64 Hz) of 1Jobsd(Se,Se) observed for RSeSeR' and large values (330-380 Hz) of 1Jobsd(Se,Se) observed for 4-substituted naphtho[1,8-c,d]-1,2-diselenoles, which correspond to synperiplanar diselenides. The HOMO-->LUMO and HOMO-1-->LUMO transitions contribute the most to 1J(Se,Se) at phi=0 and 180 degrees to give large values of 1J(Se,Se), whereas various transitions contribute and cancel each other out at phi=90 degrees to give small values of 1J(Se,Se). Large 4Jobsd(Se,Se) values were also observed in the nonbonded Se...Se, Se...Se=O, and O=Se...Se=O interactions at naphthalene 1,8-positions. The Fermi contact (FC) term contributes significantly to 4J(Se,Se), whereas the paramagnetic spin-orbit (PSO) term contributes significantly to 1J(Se,Se). 2J(Se,Se) and 3J(Se,Se) were analyzed in a similar manner and a torsional angular dependence was confirmed for 3J(Se,Se). Depending on the structure, the main contribution to (n)J(Se,Se) (n=2, 3) is from the FC term, with a lesser contribution from the PSO term. Analysis of each transition enabled us to identify and clearly visualize the origin and mechanism of the couplings.

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Synthesis and Properties of Chalcogen‐bridged Naphthalenes: A New Series of Electron Donors*

Cited by 26 publications

References 24 publications

Acid-Catalyzed Electron Transfer Processes in Naphthalene peri-Dichalcogenides

Acid-Catalyzed Electron Transfer Processes in Naphthalene peri-Dichalcogenides

Tellurium‐Containing Heterocycles as Donor Molecules

Torsional Angular Dependence of ¹J(Se,Se) and Fermi Contact Control of ⁴J(Se,Se): Analysis of ⁿJ(Se,Se) (n=1–4) Based on Molecular Orbital Theory

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Synthesis and Properties of Chalcogen‐bridged Naphthalenes: A New Series of Electron Donors*

Cited by 26 publications

References 24 publications

Acid-Catalyzed Electron Transfer Processes in Naphthalene peri-Dichalcogenides

Acid-Catalyzed Electron Transfer Processes in Naphthalene peri-Dichalcogenides

Tellurium‐Containing Heterocycles as Donor Molecules

Torsional Angular Dependence of 1J(Se,Se) and Fermi Contact Control of 4J(Se,Se): Analysis of nJ(Se,Se) (n=1–4) Based on Molecular Orbital Theory

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Torsional Angular Dependence of ¹J(Se,Se) and Fermi Contact Control of ⁴J(Se,Se): Analysis of ⁿJ(Se,Se) (n=1–4) Based on Molecular Orbital Theory