NMR spectroscopy of metal cyclopentadienyls VIII. Prototropism and dimerisations of silicon cyclopentadienyls

Studies have been made of the slow dynamic processes which occur with the silicon cyclopentadienyls C₅H₅Si(CH₃)Cl₂, such as prototropic rearrangement and dimerisation. The product formed through spontaneous dimerisation has been found to consist almost entirely of the dimer of the main vinylic isomer of C₅H₅Si(CH₃)Cl₂. The dimeric structure has been proved by means of PMR spectra (100 MHz). From kinetic studies values of the rate constants at temperatures of 20,44,55, and 65° have been obtained and an approximate plot of log kvs. (1/T)x10³, has enabled the thermodynamic characteristics of the prototropic rearrangement and of the dimerisation to be calculated. The ability of cyclopentadienyl systems to undergo hydrogen migration is discussed and the reactivity of fluxional systems is shown to be governed by the rate of metallotropic rearrangement.