Cyclopalladation of 1,1′‐Azonaphthalene (= Di(naphthalen‐1‐yl)diazene): Isolation and characterization of two isomeric complexes

Abstract

Abstract The cyclopalladation of 1,1′‐azonaphthalene (= di(naphthalen‐1‐yl)diazene; 2 ) with bis(hexafluoroacetyl‐acetonato)palladium(II) (3; [Pd(hfa) 2 ]) yields the ortho ‐palladated complex (1,1,1,5,5,5‐hexafluoropentane‐2,4‐dionato‐κ 2 O , O ′)[1‐(naphthalen‐1‐ylazo‐κ N 2 )naphthalen‐2‐yl‐κ C 2 ]palladium(II) ( 4 ) as well as the peri ‐palladated complex (1,1,1,5,5,5‐hexafluoropentane‐2,4‐dionato‐κ 2 O , O ′)[8‐(naphthalen‐1‐ylazo‐κ N 2 )naphthalen‐1‐yl‐κ C 1 ]‐palladium(II) ( 5 ); their structures were corroborated by X‐ray analyses. The formation of the novel peri ‐metallated product 5 containing a six‐membered palladacycle strongly depends upon the reaction conditions.