Abstract
The photocatalytic heterocyclotrimerisation of ethyne and nitrile initiated by cobalt(I) complexes was studied. General mechanistic features as proposed for the ‘dark’ reaction were found to apply as well under photolytic conditions albeit with modifications. The results suggest that the irradiated light accelerates that stage of reaction, leading to the organometallic species which is believed to be the common intermediate for the formation of pyridine and benzene. The rate of pyridine production is linear dependent from nitrile concentration. Benzene formation may be minimised by keeping the ethyne concentration low. An alternative mechanism, based on the initial coordination of nitrile at cobalt is not confirmed. A novel gas buret system was used, which allowed automatic feed of ethyne under isobaric conditions and to monitor all reactants simultaneously on-line.
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