Electrochemical properties of a disilene, a tetrasila-1,3-butadiene, and their germanium analogues.
The redox properties of aryl-substituted disilene (1), tetrasila-1,3-butadiene (2), digermene (3), and tetragerma-1,3-butadiene (4) (in which the aryl group is 2,4,6-triisopropylphenyl) have been studied by cyclic voltammetry (CV) in two different solvents. In o-dichlorobenzene, disilene 1 exhibited reversible redox couples in both oxidation and reduction processes, whereas tetrasilabutadiene 2 showed a reversible behavior only in its oxidation and an irreversible wave in its reduction. Tetragermabutadiene 4 afforded a reversible couple in its reduction and an irreversible wave in its oxidation, whereas digermene 3 showed only an irreversible oxidation wave but no reduction one. In comparison, all observed oxidation and reduction waves in THF were irreversible. In both solvents, the same trend of decreasing ease of oxidation has been observed: 2>4>3>1. The calculated vertical ionization energies (E(i)) for the 2,6-dimethylphenyl-substituted model compounds 9-12 afforded a trend of ease of oxidation that decreases in the series tetrasilabutadiene 10>tetragermabutadiene 12>disilene 9>digermene 11. This predicted trend parallels the measured oxidation potentials in the sense that the heavy butadienes are easier to oxidize than the heavy alkenes. The trend in the reduction direction has been found to be different in the two solvents studied. The computed electron affinities (E(ea)) for compounds 9-12 indicated that the ease of reduction decreased in the sequence tetragermabutadiene 12>tetrasilabutadiene 10>digermene 11>disilene 9. However, no straightforward relation between the computed electron affinities and the experimentally measured reduction potentials has been found.
Schäfer
Annemarie
A
Institute for Pure and Applied Chemistry, Carl von Ossietzky University Oldenburg, Carl von Ossietzky-Str. 9-11, 26211 Oldenburg (Germany), Fax. (+49) 447-798-3352.
Weidenbruch
Manfred
M
Institute for Pure and Applied Chemistry, Carl von Ossietzky University Oldenburg, Carl von Ossietzky-Str. 9-11, 26211 Oldenburg (Germany), Fax. (+49) 447-798-3352.
Müller
Thomas
T
Institute for Pure and Applied Chemistry, Carl von Ossietzky University Oldenburg, Carl von Ossietzky-Str. 9-11, 26211 Oldenburg (Germany), Fax. (+49) 447-798-3352.
Pravinkumar
Kendrekar
K
Department of Chemistry, Faculty of Natural Sciences, Ben-Gurion University of the Negev, Beer Sheva 84105 (Israel), Fax: (+972) 8-6472943.
Becker
James Y
JY
Department of Chemistry, Faculty of Natural Sciences, Ben-Gurion University of the Negev, Beer Sheva 84105 (Israel), Fax: (+972) 8-6472943.