I. Configurational stability and redistribution equilibria in organomagnesium compounds. II. Redistribution equilibria in organocadmium compounds

<p>I. CONFIGURATIONAL STABILITY AND REDISTRIBUTION EQUILIBRIA IN ORGANOMAGNESIUM COMPOUNDS</p> <p>The dependence of the rate of inversion of a dialkylmagnesium compound on the solvent has been studied. </p> <p>Examination of the temperature dependence of the nuclear magnetic resonance spectrum of 1-phenyl-2-propylmagnesium bromide in diethyl ether solution indicates that inversion of configuration at the methylene group of this Grignard reagent occurs with an approximate rate of 2 sec^-1 at room temperature. This is the first example of a rapid inversion rate in a secondary Grignard reagent.</p> <p>The rates of exchange of alkyl groups between dineopentylmagnesium and di-<u>s</u>-butylmagnesium, <u>bis</u>-(2-methylbutyl)-magnesium and <u>bis</u>-(4, 4-dimethyl-2-pentyl)-magnesium respectively in diethyl ether solution were found to be fast on the nmr time scale. However, the alkyl group exchange rate was found to be slow in a diethyl ether solution of dineopentylmagnesium and <u>bis</u>-(2-methylbutyl)-magnesium containing N, N, N', N'-tetramethylethylenediamine. The unsymmetrical species neopentyl-2-methylbutyl-magnesium was observed at room temperature in the nmr spectrum of the solution containing the diamine.</p> <p>II. REDISTRIBUTION EQUILIBRIA IN ORGANOCADMIUM COMPOUNDS</p> <p>The exchange of methyl groups in dimethylcadmium has been studied by nuclear magnetic resonance spectroscopy. Activation parameters for the methyl group exchange have been measured for a neat sample and for a solution in tetrahydrofuran. The exchange is faster in the basic solvent tetrahydrofuran relative to the neat sample and in tetrahydrofuran solution is retarded by the solvating agent N, N, N’, N’-tetramethylethylenediamine and greatly increased by cadmium bromide. The addition of methanol to a solution of dimethylcadmium in tetrahydrofuran appears to have very little effect on the rate of exchange. The exchange was found to proceed with retention of configuration. The rate-limiting step for the exchange of methyl groups in a basic solvent appears to be the dissociation of coordinating solvent from dimethylcadmium. </p> <p>The equilibrium between methylcadmium bromide, dimethylcadmium and cadmium bromide in tetrahydrofuran solution has also been studied. At room temperature the interconversion of the species is very fast on the nmr time scale but at -100° distinct absorptions for methylcadmium bromide and imethylcadmium are observed. </p> <p>The species ethylmethylcadmium has been observed in the nmr spectrum.</p> <p>The rate of exchange of vinyl groups in a solution of divinylcadmium in tetrahydrofuran has been found to be fast on the nmr time scale.</p>