Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases p. 1923 - 1936 (1982)
Update date:2022-07-30
Topics:
Caldin, Edward F.
Field, John P.
Rate and equilibrium constants have been determined over a range temperature for the reactions of zinc meso-tetraphenylporphyrin with pyridine (in chlorobenzene, 1-chlorobutane and toluene), with 2-methylpyridine (in 1-chlorobutane), and with imidazole (in 1-chlorobutane).Rates were measured by means of an improved microwave temperature-jump apparatus incorporating signal-averaging, and at low temperatures by the stopped-flow method, with spectrophotometric detection.The forward rate constants are lower by about an order of magnitude than the values calculated for diffusion control from the simple Smoluchowsky model.A two-step mechanis appears likely.Solvent and steric effects on the rate are discussed.
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