Quantitative Line-Shape Analysis of Temperature- and Concentration-Dependent 13C-NMR Spectra of 6Li- and 13C-Labelled Organolithium Compounds. Kinetic and Thermodynamic Data for Exchange Processes in Dibromomethyllithium, (Phenylthio)methyllithium,and Butyllithium

Using the ‘permutation of indices’ method proposed by Kaplan and Fraenkel, we could formulate the density-matrix equations required to fit the temperature-dependent ¹³C-NMR spectra observed with the title compounds. For ⁶Li¹³CHBr₂ ( 1 ) and ⁶Li¹³CH₂SC₆H₅ ( 2 ) an exchange mechanism is proposed by which monomers interchange C- and Li-atoms via a non-observed dimeric intermediate; the activation parameters of these intermolecular dynamic processes have been found to be ΔH^≠ = 10.2 kcal/mol, ΔS^≠ = 13.7 cal/mol·K for 1 and ΔH^≠ = 11.1 kcal/mol, ΔS^≠ = 20.6 cal/mol·K for 2 ((D₈)THF as solvent). In the case of (⁶Li)butyllithium ( 3 ), the observed low-temperature spectra indicate that dimeric ( 3b ) and tetrameric ( 3a ) species are in dynamic equilibrium interchanging the C₃HCH₂ groups (and THF molecules) bonded to the ⁶Li-atoms. The relative concentrations of the dimer and of the tetramer have been determined by peak integration or by line-shape fitting; the ‘pseudo’- equilibrium constant, defined by K′_eq = 3b ]²/ 3a ], was found to be 2.6·10^?2 mol/1 (at ?88°) and corresponds to ΔG_R (?88°) = 2 ΔG°_f( 3b ) – ΔG°_f( 3a ) = 1.34 kcal/mol. The activation parameters of the dynamic process responsible for the exchange were estimated as ΔH^≠ = 3.78 kcal/mol and ΔS^≠ = ?31.3 cal/mol·K. Tentative interpretation of the thermodynamic and kinetic parameters is given.