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Kinetics and Mechanism of Vinylation of ortho-Palladated NN-Dialkylbenzylamines by para-Substituted Styrenes

DOI: 10.1039/P29830001511

Source and publish data:

Journal of the Chemical Society. Perkin transactions II p. 1511 - 1518 (1983)

Update date:2022-08-04

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Authors:

Ryabov, Alexander D.Ryabov, Alexander D.

Sakodinskaya, Inna K.Sakodinskaya, Inna K.

Yatsimirsky, Anatoly K.Yatsimirsky, Anatoly K.

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Article abstract of DOI:10.1039/P29830001511

The kinetics of vinylation of ortho-palladated NN-dialkylbenzylamines (1a-g) by CH2=CHC6H4R3-p (R3=H,Cl, Br, Me, and MeO) to form the respective 2-dialkylaminomethylstilbenes (2) has been studied mainly at 30 deg C in acetic acid solvent.The reaction follows second-order kinetics: d<(2)>/dt=k2<(1)>.The rate constants k2 increase markedly in the presence of both alkali-metal perchlorates (MClO4) and small concentrations of perchloric acid, k2 being directly proportional to .It is shown that the salt effect originates from the solvolytic reaction MClO4 + HOAc <*> MOAc + HClO4.Conversion of dimer (1a) into the respective monomer (3) stops the reaction, but the latter species readily forms ?-complexes with styrenes.The stability constants of 1:1 ?-complexes have been determined and their Hammett correlation with a slope of -1.87 is established.For a series of substituted styrenes lgk2 is the linear function of Hammett ?p values with a slope of ca. -1.For a series of ring-substituted complexes (1) lgk2 correlates with the pKa of the parent benzylamines with a slope of 0.98.The results are interpreted in terms of a mechanism involving intermediate protonation of (1), ?-co-ordination of alkene, and subsequent rate-determining intramolecular insertion of styrene into a Pd-C bond through a four-centred transition state.

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