Chemically induced dynamic nuclear polarizations (CIDNP) and kinetic studies of the decomposition of di-t-butylmagnesium, -zinc,and -mercury

Pulsed Fourier transform NMR was used to study ¹H-CIDNP arising from the thermolysis of di-t-butylmagnesium 1 and -zinc 2 and from the thermolysis and photolysis of di-t-butylmercury 3 in deuterated hydrocarbons as solvents. The decomposition of 1, 2, and 3 leads to metal, to the polarized disproportionation products isobutane 4 and isobutene 5 (rate constant k_d), and to the unpolarized combination product 2,2,3,3-tetramethylbutane 6 (rate constant k_c). Analysis of the ratio k_d/k_c as well as the activation entropies for the decomposition establish a radical mechanism for the main process. In the decomposition of 1 and 2 an A/E multiplet polarization of 4 and 5 is observed. This is opposite to the E/A polarization of these products arising during the thermolysis of 3. The photolysis of 3, however, leads to an A/E polarization of 4 and 5. The different phases of the multiplets indicate a decomposition of dialkylmercury in a cage reaction. Dialkylmagnesium and -zinc, however, decompose in a free-radical reaction of uncorrelated t-butyl pairs.