Pyrolysis of dimethylzinc and dimethylzinc-d6 by the toluene carrier method

Abstract

The pyrolysis of dimethylzinc has been studied over the temperature range 823–1015 °K using toluene to alkyl ratios from 51:1 to 121:1 and total pressure of 17 to 169 mm. The decomposition occurs in two steps[Formula: see text]By extrapolation to infinite pressure[Formula: see text]and at 10 cm pressure[Formula: see text]Assuming E2 must be increased by 2–4 kcal mole−1 to obtain E2 at infinite pressure D1 + D2 = 88 ± 4 kcal mole−1; cf. 86 ± 3 kcal mole−1 from thermochemistry. When dimethylzinc-d6 is used only traces of CD4 are produced. This indicates that the non free radical decomposition of methylzinc, suggested by the results of a previous sealed ampoule study, is not a significant process under the present experimental conditions.