Summary
The reactions of nickel and copper vapours with mono-halobenzenes to form benzene and biphenyl are reported. Benzene formation apparently proceeds through the intermediacy of the phenyl radical, which is produced when metal clusters abstract halogen from the halobenzene. Biphenyl formation proceedsvia an oxidative insertion/disproportionation/reductive elimination sequence, and requires that metal atoms, rather than metal clusters, initiate the reaction sequence. The concentration of the metal in the matrix determines the pathway of the reaction. Cluster formation and benzene production are favouted by high metal concentrations, while low metal concentrations in the matrix favour biphenyl production. Copper vapours are anomalously less reactive than nickel vapours, even though copper reagents are used in the Ullmann reaction to produce biaryls through the coupling of haloarenes. This result appears to be due to the preferential formation of atoms or very small clusters over large clusters or crystallites under the conditions of the metal vapour synthesis technique.
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Douglass, S.E., Massey, S.T., Woolard, S.G. et al. Reductiveversus coupling pathways in the reactions of nickel and copper vapours with the mono-halobenzenes. Transition Met Chem 15, 317–324 (1990). https://doi.org/10.1007/BF01061941
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DOI: https://doi.org/10.1007/BF01061941