Dilithium Derivative of Tetraphenylsilole: An .eta.1-.eta.5 Dilithium Structure

West, Robert; Sohn, Honglae; Bankwitz, Uwe; Calabrese, Joseph C.; Apeloig, Yitzhak; Mueller, Thomas

doi:10.1021/ja00151a038

Cited by 174 publications

(93 citation statements)

References 3 publications

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“…Yet, despite the 6π-electron systems, the geometries of various siloles indicate that cyclic conjugation is modest. 25,26 In this context it is noteworthy that the electronic structure of siloles is valence isolobal to that of pentafulvenes ( Figure 3), cross-π-conjugated hydrocarbons in which the optical properties and degree of aromaticity can be varied extensively through substitution, from the nonaromatic parent pentafulvene to the aromatic compound when the exocyclic substituent are amino groups. Our hypothesis is now that 1 is a useful template for the design of neutral cyclic crosshyperconjugated molecules.…”

Section: -24mentioning

confidence: 99%

1,4-Disilacyclohexa-2,5-diene: a molecular building block that allows for remarkably strong neutral cyclic cross-hyperconjugation

et al. 2014

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M. et al. (2014) 1,4-Disilacyclohexa-2,5-diene: a molecular building block that allows for remarkably strong neutral cyclic cross-hyperconjugation. Table-of-contentsThe fusion of two cross-hyperconjugated segments in form of the small 1,4-disilacyclohexa-2,5-diene cycle provides for electronic and optical properties which resemble to those of π-conjugated cycles.2 Abstract: The electronic structures of 2,3,5,6-tetraethyl-1,4-disilacyclohexa-2,5-dienes with either four chloro (1a), methyl (1b), or trimethylsilyl (TMS) (1c) substituents at the two silicon atoms were examined in an effort to design cyclic compounds with strong neutral cross-hyperconjugation between π-and σ-bonded segments. Remarkable variations in the lowest electronic excitation energies, lowest ionization energies, and the first oxidation potentials were observed upon change of substituents, as determined by gas phase ultraviolet 3

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Section: -24mentioning

confidence: 99%

1,4-Disilacyclohexa-2,5-diene: a molecular building block that allows for remarkably strong neutral cyclic cross-hyperconjugation

et al. 2014

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“…The color of the solution changed to dark red. After allowing to stand for 5 min, the 119 Sn signal assignable to (Ph 2 Sn) 6 (4) by quenching with methyl iodide (Scheme 2). The signal for 1,1-dilithiostannane was not observed.…”

Section: Nmr Study Of the Reduction Of Dichlorodiphenylstannane With mentioning

confidence: 99%

Reduction of dichlorodiphenylstannane

Saito

Okamoto

Yoshioka

2005

Appl. Organometal. Chem.

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“…Since silole and germole dianions (RC) 4 Si 2− and (RC) 4 Ge 2− , R=Ph and Me, have been studied by X-ray crystallography, [3][4][5][6] siloles and germoles are of considerable current interest, both because of their unusual electronic and optical properties 18,19 Si NMR spectra, however its crystal structure has not been reported to date.…”

Section: 17mentioning

confidence: 99%

Inversion Barriers of Methylsilole and Methylgermole Monoanions

Pak¹,

Ko²,

Sohn³

2012

Bulletin of the Korean Chemical Society

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Density functional MO calculations for the methylsilole anion of [C4H4SiMe]− and methylgermole anion of [C4H4GeMe] − at the B3LYP (full)/6-311+G* level (GAUSSIAN 94) were carried out and characterized by frequency analysis. The ground state structure for the methylsilole anion and methylgermole anion is that the methyl group is pyramidalized with highly localized structure. The difference between the calculated Cα-Cβ and Cβ-Cβ distances are 9.4 and 11.5 pm, respectively. The E-Me vector forms an angle of 67.9 o and 78.2 o with the C4E plane, respectively. The optimized structures of the saddle point state for the methylsilole anion and methylgermole anion have been also found as a planar with highly delocalized structure. The optimized Cα-Cβ and Cβ-Cβ distances are nearly equal for both cases. The methyl group is located in the plane of C4E ring and the angle between the E-Me vector and the C4E plane for the methylsilole anion and methylgermole anion is 2.0 o and 2.3 o , respectively. The energy difference between the ground state structure and the transition state structure is only 5.1 kcal mol −1 for the methylsilole anion. However, the energy difference of the methylgermole anion is 14.9 kcal mol −1 , which is much higher than that for the corresponding methylsilole monoanion by 9.8 kcal mol . Based on MO calculations, we suggest that the head-to-tail dimer compound, 4, result from [2+2] cycloaddition of silicon-carbon double bond character in the highly delocalized transition state of 1. However, the inversion barrier for the methylgermole anion is too high to dimerize.

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Dilithium Derivative of Tetraphenylsilole: An .eta.1-.eta.5 Dilithium Structure

Cited by 174 publications

References 3 publications

1,4-Disilacyclohexa-2,5-diene: a molecular building block that allows for remarkably strong neutral cyclic cross-hyperconjugation

1,4-Disilacyclohexa-2,5-diene: a molecular building block that allows for remarkably strong neutral cyclic cross-hyperconjugation

Reduction of dichlorodiphenylstannane

Inversion Barriers of Methylsilole and Methylgermole Monoanions

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