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- W2024551189 abstract "The reactions of triphenylsilyl-sodium(Ph 3 SiNa), diphenylmethylsilyl-sodium(Ph 2 MeSiNa), triphenylsilyl-potassium (Ph 3 SiK), triphenylsilyl-rubidium (Ph 3 SiRb), and triphenylsilyl-caesium (Ph 3 SiCs) with 9-methylfluorene in tetrahydrofuran (THF) were studied using the stop-flow technique at low temperatures. The rate constant k (1 mol −1 s −1 ) depends on the nature of the cation; at −50 °C k is 11.5 for Ph 3 SiNa, 29.5 for Ph 2 MeSiNa, 26.8 for Ph 3 SiK, 35.6 for Ph 3 SiRb, and 47.9 for Ph 3 SiCs. It seems that the organosilylalkali–metal compounds (R 3 SiM) exist in the form of contact ion-pair and therefore the reactivity of an ion-pair is determined by the Coulombic binding energy of the pair. The thermodynamic constants of activation for these reactions were calculated for −50 °C and compared with the corresponding values of triphenylsilyl-lithium Ph 3 SiLi reaction with 9-methylfluorene in THF. The plots of log k, ΔS ≠ , and ΔH ≠ against 1/(r c + 2) and ΔS ≠ against ΔH ≠ were drawn to show that Li + due to its existence as solvent separated ion-pair behaves differently to its Na + , K + , Rb + , and Cs + counterparts.The electronic spectra of R 3 SiM, 9-methyl-fluoren-9-yl-sodium, -potassium, -rubidium and -caesium were determined at temperatures varying from 20 to −80 °C. A red shift was observed in spectra of R 3 SiNa at low temperatures; this was attributed to the increase in dipole moment which occurs during the electronic transition. The spectra of 9-methylfluoren-9-yl-sodium, -potassium, -rubidium, and -caesium were compared with their lithium counterpart to explain the effects of gegenion on the solvation of these species." @default.
- W2024551189 created "2016-06-24" @default.
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- W2024551189 date "1973-08-15" @default.
- W2024551189 modified "2023-09-23" @default.
- W2024551189 title "The Reactions of Organometallic Compounds Involving Silicon. Reactions of Methyldiphenyl-, Triphenylsilyl-sodium, -potassium, -rubidium, and -caesium with 9-Methylfluorene in Tetrahydrofuran" @default.
- W2024551189 doi "https://doi.org/10.1139/v73-412" @default.
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