Journal of the Chemical Society, Dalton Transactions p. 545 - 550 (1994)
Update date:2022-09-26
Topics:
Gonzalez, Gabriel
Lahuerta, Pascual
Martinez, Manuel
Peris, Eduardo
Sanau, Mercedes
Compounds of general formula a facile cyclometallation reaction, catalysed in the presence of protic acids, to give doubly metallated compounds A mechanism in which protons facilitate loss of one of the acetate groups in the starting compounds is proposed.Preliminary experiments showed that the addition of phosphines enhances the cyclometallation rate.The mechanism is fully concerted with a highly ordered transition state as seen by the very negative activation entropies.The values obtained for the deuterium kinetic isotopic effect indicate that, for the acid-catalysed path, the transition state lies in a more advanced position on the reaction coordinate than for the thermal process.The gap between the isokinetic plots for the acid-catalysed and thermal reactions is ca. 20 kJ mol-1.
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