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Silyl‐Substituted Carbocations

1998; Wiley; Linguagem: Inglês

10.1002/0470857250.ch12

2042-5651

Hans‐Ullrich Siehl, Thomas Müller,

Inorganic and Organometallic Chemistry

This chapter contains sections titled: Introduction Calculational Results Gas Phase Studies α-substitution β-substitution Solvolytic Studies α-silicon-substituted Carbocations in Solvolysis β-silicon-substituted Carbocations in Solvolysis α-disilanyl Carbocations in Solvolysis γ-silicon Effect δ-silicon Effect Stable Ion Studies α-silyl Substitution NMR Spectroscopic Characterization of α-silyl-substituted Carbocations 1-phenyl-1-trimethylsilylethyl Cation Diphenyl(trimethylsilyl)methyl Cations X-ray Structure Analysis of the Tris(trimethylsilyl)cyclopropenylium Cation β-silyl-substituted Carbocations sp2-hybridized Carbocations Photochemical Generation and UV Characterization of Transient β-silyl-substituted Carbocations 9-(Trimethylsilylmethyl)fluoren-9-yl Cations Silyl-substituted Cyclohexadienyl Cations X-ray Crystallographic Study of β-silylcyclohexadienyl Cations NMR Spectroscopic Characterization of β-silyl-substituted Carbocations β-silyl-substituted Secondary p-methoxybenzyl Cations 1-p-anisyl-2-triisopropylsilylethyl Cations Other β-silyl-substituted Secondary Benzyl Cations β-silyl-substituted Tolyl- and Phenylmethyl Cations 1-ferrocenyl-2-triisopropylsilylethyl Cations β-silyl-substituted Tertiary Benzyl Cations 1,1-diphenyl-2-(triethylsilyl)ethyl Cations β-silyl-substituted Allyl Cations 2-[1′-(Trimethylsilyl)ethenyl]adamant-2-yl Cations sp-hybridized Carbocations (Vinyl Cations) β-silyl-substituted Dienyl Cations β-silyl-substituted α-arylvinyl Cations α-ferrocenyl-β-silyl-substituted Vinyl Cations α-mesityl-β-silyl-substituted Vinyl Cations α-tolyl- and α-phenyl-β-silyl-substituted Vinyl Cations α-anisyl-β-silyl-substituted Vinyl Cations The 1-bis(trimethylsilyl)methyl-2-bis(trimethylsilyl)ethenyl Cation Silyl-substituted Hypercoordinated Carbocations The α-and-γ-silyl Effect in Bicyclobutonium Ions 1-(Trimethylsilyl)bicyclobutonium Ion 3-endo-(Trialkylsilyl)bicyclobutonium Ions Silanorbornyl Cation The 6,6-dimethyl-5-neopentyl-6-sila-2-norbornyl Cation Conclusions Acknowledgements References