Abstract: | The solution structure and the aggregation behavior of (E)-2-lithio-1-(2-lithiophenyl)-1-phenylpent-1-ene ( 1 ) and (Z)-2-lithio-1-(2-lithiophenyl)ethene ( 2 ) were investigated by one- and two-dimensional 1H-, 13C-, and 6Li-NMR spectroscopy. In Et2O, both systems form dimers which show homonuclear scalar 6Li,6Li spin-spin coupling. In the case of 2 , extensive 6Li,1H coupling is observed. In tetrahdrofuran and in the presence of 2 mol of N,N,N′,N′-tetramethylethylylenediamine (tmeda), the dimeric structure of 1 coexists with a monomer. The activation parameters for intra-aggregate exchange in the dimers of 1 and 2 ( 1 (Et2O): ΔH≠ = 62.6 ± 13.9 kJ/mol, ΔS≠ = 5.8 ± 14.0 J/mol K, ΔG≠(263) = 61.1 kJ/mol; 2 (dimethoxyethane): ΔH≠ = 36.9 ± 6.5 kJ/mol, ΔS≠ = ?61 ± 25 J/mol K, ΔG≠(263) = 54.0 kJ/mol) and the thermodynamic parameters for the dimer-monomer equilibrium for 1 (ΔH°; = 26.7 ± 5.5 kJ/mol, ΔS° = 63 ± 27 J/mol K), where the monomer is favored at low temperature, were determined by dynamic NMR studies. |