Palladium(II) allylic complexes by carbene transmetalation and migratory insertion reactions: Synthesis and side reactions

New 1,1-alkoxy, aryl substituted palladium η3-allyls [Pd(μ-Br){η3-C(C6F5)(OMe)CHR1CHR2}]2 can be synthesized from [W(CO)5{C(OMe)CHR1double bond; length as m-dashCHR2}] and a palladium perfluoroaryl complex. The allyls are formed by transmetalation of the carbene fragment followed by migratory insertion of C6F5 to the putative and highly reactive Pd carbene complex. This reaction pathway predominates in all cases, but insertion of the double bond of the tungsten alkoxyvinylcarbenes into the Pd–C6F5 bond leads to secondary products, namely C6F5(OMe)Cdouble bond; length as m-dashCR1CH(C6F5)R2.