Article Dans Une Revue Dalton Transactions Année : 2010

DFT study of the mechanism of benzocyclobutene formation by palladium-catalysed C(sp3)-H activation: role of the nature of the base and the phosphine.

Résumé

DFT(B3PW91) calculations of the mechanism of the intramolecular C(sp(3))-H arylation of 2-bromo-tert-butylbenzene to form benzocyclobutene catalysed by Pd(PR(3)) (R = Me, (t)Bu) and a base (acetate, bicarbonate, carbonate) show that the preferred mechanism is highly dependent on the nature of the phosphine and the base used in the calculations. With the experimental reagents (P(t)Bu(3) and carbonate) the rate-determining step is C-H activation with the base coordinated trans to the C-H bond. An agostic interaction of a geminal C-H bond with respect to the bond to be cleaved induces a lowering of the activation barrier.

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Dates et versions

hal-00691421 , version 1 (26-04-2012)

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Citer

Christos E. Kefalidis, Olivier Baudoin, Eric Clot. DFT study of the mechanism of benzocyclobutene formation by palladium-catalysed C(sp3)-H activation: role of the nature of the base and the phosphine.. Dalton Transactions, 2010, 39 (43), pp.10528-35. ⟨10.1039/c0dt00578a⟩. ⟨hal-00691421⟩
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