The complexes [Pd(η2-dmfu)(P–N)] [P–N = 2-(PPh2)C6H4-1-CHNR, R = C6H4OMe-4; CHMe2; C6H3Me2-2,6; C6H3(CHMe2)-2,6] react with an excess of BrC6H4R1-4 (R1 = CF3; Me) yielding the oxidative addition products [PdBr(C6H4R1-4)(P–N)] at different rates depending on R [C6H4OMe-4 > C6H3(CHMe2)-2,6 > CHMe2
≈ C6H3Me2-2,6] and R1 (CF3
≫ Me). In the presence of K2CO3 and activated olefins (ol = dmfu, fn), the latter compounds react with an excess of 4-R2C6H4B(OH)2 (R2 = H, Me, OMe, Cl) to give [Pd(η2-ol)(P–N)] and the corresponding biaryl through transmetallation and fast reductive elimination. The transmetallation proceeds via a palladium(II) intermediate with an O-bonded boron anion, the formation of which is markedly retarded by increasing the bulkiness of R. The intermediate was isolated for R = CHMe2, R1 = CF3 and R2 = H. The boron anion is formulated as a diphenylborinate anion associated with phenylboronic acid and/or as a phenylboronate anion associated with diphenylborinic acid. In general, the oxidative addition proceeds at a lower rate than transmetallation and represents the rate-determining-step in the coupling reaction of aryl bromides with arylboronic acids catalyzed by [Pd(η2-dmfu)(P–N)].
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