TY - JOUR
T1 - Formation of separated versus contact ion pairs in alkali metal thiolates and selenolates
AU - Chadwick, Scott
AU - Englich, Ulrich
AU - Ruhlandt-Senge, Karin
AU - Watson, Charles
AU - Bruce, Alice E.
AU - Bruce, Mitchell R.M.
PY - 2000
Y1 - 2000
N2 - The solvation and ligation tendencies of alkali metal thiolates and selenolates in relation to metal and donors were investigated by synthesizing a family of target compounds, and analysing their structural features in solution and the solid state. The target compounds were synthesized utilizing hydrogen elimination, involving treatment of the chalcogenol with either sodium or potassium hydride in the presence of various donors. The separated ions were [Na(18-crown-6)(THF)2][SMes*] 1, (Mes* = 2,4,6-tBu3C6H2), [K(18-crown-6)(THF)2][SMes*] 3, and [K(18-crown-6)(THF)2][SeMes*] 4, and K(dibenzo-18-crown-6)(SMes*)·THF 2, displayed potassium-sulfur contacts. Compounds 1-4 were characterized using X-ray crystallography, NMR and IR spectroscopy. Cyclic voltammetry studies were carried out on 1-3, Na(dibenzo-18-crown-6)(SMes*) 5 and K(dibenzo-18-crown-6)(STrip)· THF 6 (Trip = 2,4,6-iPr3C6H2). A concentration dependent equilibrium reaction, which leads to an increase in free thiolate at higher concentrations, was observed for all complexes. NMR experiments using solutions of 5 (8.5 and 0.085 mM, THF-d8) and trimethyl phosphate confirmed the presence of free thiolate at higher concentration.
AB - The solvation and ligation tendencies of alkali metal thiolates and selenolates in relation to metal and donors were investigated by synthesizing a family of target compounds, and analysing their structural features in solution and the solid state. The target compounds were synthesized utilizing hydrogen elimination, involving treatment of the chalcogenol with either sodium or potassium hydride in the presence of various donors. The separated ions were [Na(18-crown-6)(THF)2][SMes*] 1, (Mes* = 2,4,6-tBu3C6H2), [K(18-crown-6)(THF)2][SMes*] 3, and [K(18-crown-6)(THF)2][SeMes*] 4, and K(dibenzo-18-crown-6)(SMes*)·THF 2, displayed potassium-sulfur contacts. Compounds 1-4 were characterized using X-ray crystallography, NMR and IR spectroscopy. Cyclic voltammetry studies were carried out on 1-3, Na(dibenzo-18-crown-6)(SMes*) 5 and K(dibenzo-18-crown-6)(STrip)· THF 6 (Trip = 2,4,6-iPr3C6H2). A concentration dependent equilibrium reaction, which leads to an increase in free thiolate at higher concentrations, was observed for all complexes. NMR experiments using solutions of 5 (8.5 and 0.085 mM, THF-d8) and trimethyl phosphate confirmed the presence of free thiolate at higher concentration.
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U2 - 10.1039/b000665n
DO - 10.1039/b000665n
M3 - Article
AN - SCOPUS:0008181426
SN - 1470-479X
SP - 2167
EP - 2173
JO - Journal of the Chemical Society, Dalton Transactions
JF - Journal of the Chemical Society, Dalton Transactions
IS - 13
ER -