Gehinderte ligandenbewegungen in übergangsmetallkomplexen : V. 1H-NMR-untersuchung der bewegungen des olefinliganden in cyclopentadienyl-mangan-dicarbonyl-tetramethoxyäthylen

The methoxy signals in the ¹H NMR spectrum of cyclopentadienylmanganese dicarbonyl tetramethoxyethylene, C₅H₅Mn(CO)₂[C₂(OCH₃)₄], show a definite temperature-dependence. In CS₂ solution the variations of the signals are observed within a single temperature range, while in toluene-d₈ two regions of change are found to exist. These data are explained on the basis of two mutually independent ligand movements: a hindered rotation of the olefin ligand around the metalligand bond (ΔG³₁₉₄ = 9.8 ± 0.6 kcal/mol), and a hindered movement of the four methoxy groups (ΔG³₂₆₃ = 13.8 ± 0.3 kcal/mol, both in toluene-d₈. Chiral conformations of the ligand are assumed to be formed when the movement of the methoxy substituents ceases.