Incorporation of PdCl₂P₂ Complexes in Ni‐MOF for Catalyzing Heck Arylation of Functionalized Olefins

Abstract

Two palladium complexes of a PdCl 2 P 2 type with P = tri(1‐piperidinyl)phosphine (Pd‐1) and triphenylphosphine (Pd‐2) were successfully immobilized on [Ni 8 (OH) 4 (OH 2 ) 2 (L) 6 ] n (Ni‐MOF) material [L=4,4′‐(benzene‐1,4‐diyldiethyne‐2,1‐diyl)bis(1‐H‐pyrazole)] to form Pd@Ni‐MOF composites. The presence of big octahedral cavities in the Ni‐MOF structure (2.4 nm) enabled incorporation of PdCl 2 P 2 molecules inside the Ni‐MOF, as confirmed by physicochemical measurements and computer simulation. The Pd@Ni‐MOF composites catalyzed arylation of estragole by iodobenzene with an efficiency higher than that for the corresponding PdCl 2 P 2 compounds without MOF. Arylation of eugenol by PhB(OH) 2 unexpectedly resulted in the formation of ether as the main product. This was explained by the dominating activity of the Cu@MOF catalyst, formed in situ under the reaction conditions.