Electrochemical and alkali metal reduction studies of silicon, germanium, and tin derivatives of cyclooctatetraene

Paquette, Leo A.; Wright, C. David; Traynor, Sean G.; Taggart, Davis L.; Ewing, Gary D.

doi:10.1016/0040-4020(76)85191-5

Cited by 18 publications

(20 citation statements)

References 32 publications

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“…The CT process is discussed on the basis of calculated structures, spacer-induced electronic perturbations of the COT rings, and spacer-and cation-mediated interactions between donor and acceptor moieties. An unusual selective differential broadening of 13 C NMR peaks of the carbons of the dianion ring of the dipotassium salts of 1 2Ϫ , 2 2Ϫ , CH 3 COT 2Ϫ (3 2Ϫ -2K + ) and (CH 3 ) 3 SiCOT 2Ϫ (4 2Ϫ -2K + ) is also reported and discussed.…”

Section: Introductionmentioning

confidence: 83%

“…1 H NMR ([ 2 H 8 ]THF, 0.49 M, 27 ЊC): δ 6.04 (H-2, br s, 2H), 5.92 (d, 2H, J = 11.4 Hz), 5.85 (dd, 2H, J = 2.6, 11.0 Hz), 5.77-5.63 (m, 8H), 0.14 (methyl, s, 6H). 8 13 C NMR ([ 2 H 8 ]THF, 0.49 M, 27 ЊC): δ 147.31 (C-1), 141.37 (C-2), 135.51 (C-8), 133.92, 132.70, 132.17, 132.13 (C-5), 129.97, Ϫ3.34 (CH 3 ). 8 Tetrahydrofuran-d 8 ([ 2 H 8 ]THF ) was purchased from Glaser AG Basel and used without further purification.…”

Section: Perkinmentioning

confidence: 99%

“…Details of this procedure are given elsewhere. 8, 9 The progress of reduction was followed by 1 H NMR and (in some cases) by 13 C NMR spectroscopy. Because of extensive disproportionation of the radical anion to the neutral compound and dianion, 5 reduction does not have to proceed until exactly two equiv.…”

Section: Perkinmentioning

confidence: 99%

“…At room temperature 1 and 2 show 1 H NMR signals from the COT-ring hydrogens in the region of δ 5.5-6.1 and eight 13 C NMR resonances in the region of δ 129-147 (Table 1). The H-2 resonances for the two compounds were easily assigned since these appear as singlets (J 23 is small).…”

Section: Nmr Signal Assignmentmentioning

confidence: 99%

“…8,11 Intramolecular two-electron-cation transfer in such species is relatively slow, with k CT in the range of 10 Ϫ2 -10 2 s Ϫ1 at ambient temperature, which is explained by the requirement for flattening the neutral ring. Rate constants have been obtained by 1 H and 13 C dynamic NMR methods. In this study, we compare the BS kinetics for COT-CH 2 -COT (1) and COT-Si(CH 3 ) 2 -COT (2) and the BS and intramolecular CT kinetics for the corresponding dipotassium salts 1 2Ϫ -2K + and 2 2Ϫ -2K + (Fig.…”

Section: Introductionmentioning

confidence: 99%

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Bond shift and charge transfer dynamics in methylene- and dimethylsilyl-bridged dicyclooctatetraene dianions

Boman

Eliasson

Grimm

et al. 2001

J. Chem. Soc., Perkin Trans. 2

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The rate constants for bond shift in dicyclooctatetraenylmethane (1), dicyclooctatetraenyldimethylsilane (2), and their dianions (1 2Ϫ and 2 2Ϫ ) in [ 2 H 8 ]THF, have been determined from the temperature dependence of their 13 C NMR linewidths. The corresponding parameters for intramolecular electron and cation transfer (charge transfer) between the dinegative and neutral rings have been measured by 13 C NMR spin saturation transfer experiments for the dipotassium salts of 1 and 2. Selected structural features of the neutral compounds and the dianions are discussed on the basis of 13 C NMR chemical shifts and ab initio molecular orbital calculations at the HF/6-31G* and HF/3-21G(*) levels of theory. Energy contributions to the ring flattening in the bond shift process are calculated by molecular mechanics methods. The measured rate constants for both bond shift and charge transfer are larger for the methylene-bridged dianion. Approximately half of this difference is due to the greater ease of "gating" (i.e., ring flattening and distortion to the bond shift transition state) in 1 2Ϫ -2K + . A significant portion of the remainder is attributed to a greater inter-ring through-space interaction in 1 2Ϫ , although mediation by the cation and/or throughbridge interactions probably also contribute to some extent. A temperature-dependent differential 13 C NMR line broadening is observed for the dianion ring carbons of the dipotassium salts. Possible mechanisms for this counterion-specific line broadening, which occurs only for carbons with large HOMO coefficients, are discussed.

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Section: Introductionmentioning

confidence: 83%

Section: Perkinmentioning

confidence: 99%

Section: Perkinmentioning

confidence: 99%

Section: Nmr Signal Assignmentmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Bond shift and charge transfer dynamics in methylene- and dimethylsilyl-bridged dicyclooctatetraene dianions

Boman

Eliasson

Grimm

et al. 2001

J. Chem. Soc., Perkin Trans. 2

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The Electrochemistry of Alkyl Compounds of Germanium, Tin and Lead

Michman

2009

Patai's Chemistry of Functional Groups

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Terms and Abbreviations Introduction Electrosynthesis of Alkylmetallic Compounds Anodic Alkylation Cathodic Synthesis Electrodic Reactions of Group 14 Alkylmetals Analysis Complexes of Group 14 Metals Electrodic Reactions of Bimetallic Metalalkyls and Aryls Compounds with Macrocyclic Ligands Group 14 Elements in Cluster Compounds Electrocatalysis Mechanistic Studies of Electron Transfer, Concerning Organic Compounds of Group 14 Elements Effect of Group 14 Atoms on Energy Levels of Proximal Bonds Polymers Technical Applications of Special Materials

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Electrochemistry of Organosilicon Compounds

Fuchigami

2009

Patai's Chemistry of Functional Groups

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Electrochemical and alkali metal reduction studies of silicon, germanium, and tin derivatives of cyclooctatetraene

Cited by 18 publications

References 32 publications

Bond shift and charge transfer dynamics in methylene- and dimethylsilyl-bridged dicyclooctatetraene dianions

Bond shift and charge transfer dynamics in methylene- and dimethylsilyl-bridged dicyclooctatetraene dianions

The Electrochemistry of Alkyl Compounds of Germanium, Tin and Lead

Electrochemistry of Organosilicon Compounds

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