MULTIELEMENT NMR AND ELECTRON-SPIN-RESONANCE STUDY OF SOLUTIONS OF THE ALKALI-METALS NA TO CS IN N,N-DIETHYLACETAMIDE, N,N-DIPROPYLACETAMIDE, N,N-DIMETHYLPROPANAMIDE, AND TETRAMETHYLUREA

Journal article

Metal solutions of sodium through cesium in the title amide and urea solvents have been examined by multielement NMR and ESR spectroscopy. Characteristic 23Na NMR spectra of the sodide anion in the solvents N,N-diethylacetamide, N,N-dipropylacetamide, and N,N-dimethylpropanamide are reported. Solutions of the heavier alkali metals K through Cs in these three solvents showed no evidence of genuine alkalide ions. The corresponding ESR spectra of the liquid metal solutions show only a singlet resonance arising from a time-average of the signals from the solvated electron, es-, and the ion-pair species, Ms+es-. In contrast, metal solutions prepared at room temperature and then quenched in liquid nitrogen exhibit signals from both these species: a singlet due to the corresponding trapped electron and resolved hyperfine coupling to the alkali metal due to the presence of the electron-cation encounter species (Ms+es-) in these vitreous solids. Our NMR and ESR data are discussed in terms of the various chemical equilibria occurring in the metal solutions. Finally, we consider how these potential reducing species may be implicated both in dissolving metal reduction (DMR) reactions and also in the mode of decomposition of the metal solutions themselves. © 1985 American Chemical Society.

Authors: Holton, D; Edwards, P; Johnson, D; Page, C; Mcfarlane, W

• Publication status: Published
• Journal: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
• Volume: 107
• Issue: 23
• Pages: 6499-6504
• Publication date: 1985-01-01
• DOI: 10.1021/ja00309a013
• ISSN: 0002-7863
• Language: English