Kinetics and mechanism of ortho-palladation of ring-substituted NN-dimethylbenzylamines

DOI: 10.1039/DT9850002629

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Journal of the Chemical Society, Dalton Transactions p. 2629 - 2638 (1985)

Update date:2022-08-03

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Authors:

Ryabov, Alexander D.

Sakodinskaya, Inna K.

Yatsimirsky, Anatoly K.

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Article abstract of DOI:10.1039/DT9850002629

Addition of excess of NN-dimethylbenzylamine to a chloroform solution of leads to instantaneous depolymerisation of the trimer giving the monomer trans-.Reversible dissociation of the amine from the latter affords a pseudothree-co-ordinate 14-electron intermediate which undergoes subsequent rate-limiting ortho-palladation to form the cyclopalladated acetato-bridged dimer <2>.The rate-limiting step is electrophilic in character; the slope ofthe corresponding Hammett plot for differently ring-substituted NN-dimethylbenzylamines is -1.6.The kinetic isotope effect, k_H/k_D', for PhCH2NMe2 is 2.2+/-0.2.The activation entropy for the ratelimiting step is very negative, ca. -250 J K^-1 mol^-1 for PhCH2NMe2, suggesting a highly ordered tight transition state.This dissociative path is a factor of ca. 100 faster than a parallel one, involving the 16-electron monomer trans- but without loss of the amine.Ortho-palladation is not rate-limiting in acetic acid solvent, where slow cleavage of acetate bridges in polynuclear palladium species occurs, affording a vacant co-ordination site for subsequent rapid ortho-palladation.A comparison of intra- and inter-molecular activations of carbon-hydrogen bonds in arenes by palladium(II) in terms of 'effective molarities' shows that the ratio k_intra/k_inter is not less than 3.6*10² mol dm^-3.

Full text of DOI:10.1039/DT9850002629

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