Interaction of π-bonds of the silicon-silicon triple bond with alkali metals: An isolable anion radical upon reduction of a disilyne

The reduction of 1,1,4,4-tetrakis[bis(trimethylsilyl)methyl]-1,4-diisopropyltetrasila-2-yne 1 with an equivalent amount of alkali metal (Li, Na, K, KC(8)) in THF produced the corresponding disilyne anion radicals 2a-c. Their EPR spectra are independent of the metals used in THF, indicating that the disilyne anion radical species exists as solvent-separated ion pairs in polar solvents. The one-electron reduction also occurred with potassium in toluene to produce the potassium salt of the anion radical 3, which was isolated as extremely air- and moisture-sensitive dark brown crystals. The molecular structure of 3 was established by X-ray crystallography, which showed that the potassium ion is solvated by one toluene molecule. The EPR spectrum of 3 in toluene showed the interaction of the anionic silicon atom with the K(+) ion. (C) 2009 Elsevier B.V. All rights reserved.