PREPARATION AND THERMAL-DECOMPOSITION OF N-ALKYL(TRI-N-BUTYLPHOSPHINE)SILVER(I) REAGENTS
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Several primary and secondary alkyl(tri-n-butylphosphine)silver(I) compounds have been prepared by reaction between the corresponding organolithium or -magnesium reagents and iodo- or bromo(tri-n-butylphosphine) silver(I) in diethyl ether at 78. The thermal decomposition of these substances occurs rapidly at temperatures between 50 and 0 to yield hydrocarbon products derived from the alkyl group, silver(O), and tri-n-butylphosphine. Examination of the hydrocarbon products of the thermal decomposition of -butyl(tri-n-butylphosphine) silver(I) (1) and comparison of these products with those obtained on photolytic decomposition of 1 and on thermal and photolytic decomposition of 1 in the presence of 2,2,6,6-tetramethylpiperidoxyl radical (TMPO) indicate that thermal decomposition takes place predominantly by a process in which carbon-carbon bond formation, generating octane, is concerted with carbon-silver bond breaking. Intermediate free n-butyl radicals and silver(I) hydride are not important intermediates in this decomposition, although radicals are strongly implicated in reactions of 1 in the presence of light or TMPO. The thermal decomposition of sec-butyl(tri-n-butylphosphine)-silver(I) occurs by a different path, possibly involving silver hydride elimination. 1974, American Chemical Society. All rights reserved.
