| Abstrakt: |
The reactions of palladium−iminoacyl complexes with isocyanates (RNCO) and isothiocyanates (RNCS) have been investigated. The reaction of Pd{C(Me)&dbd;NXy}(Cl)(P−P) (P−P = dppe, 1; dppp, 2) with RNCE (E = O, S) in the presence of AgBF4 yields the novel compounds [Pd{C(&dbd;CH2)N(Xy)C(&dbd;E)NHR}(dppe)][BF4] (E = O and R = Et, 3; Ph, 4; E = S and R = Me, 5; Ph, 6); the formation of these complexes results from an addition reaction followed by the migration of a proton from the methyl group in the imidoyl fragment to the nitrogen in the RNCE moiety. In contrast, the reaction between Pd{C(Ph)&dbd;NXy}(I)(dppe) and RNCO in the presence of AgBF4 yields the addition product [Pd{C(Ph)&dbd;N(Xy)C(&dbd;O)(&dbd; NPh)}(dppe)][BF4] (10). Protonation of the imidoyl group in Pd{C(Me)&dbd;NXy}(Cl)(dppe) suppresses the addition reaction when the protonated complex is reacted with RNCS; the products obtained in this case are [Pd{C(Me)&dbd;NHXy}(dppe)(S&dbd;C&dbd;NR)][BF4]2 (R = Me, 15; Ph, 16). |
