Palladium(II) Aryloxides of Pd(2,6-(CH2NMe2)2C6H3)(OC6H4-X-p) (X = Me, NO2): Synthesis, Property and Reactivity towards Diphenyliodium Chloride

Abstract

para-Substituted phenoxide derivatives of Pd(II) having an NCN pincer, Pd(NCN)(-p-X) (NCN = 2,6-; X = (1), Me (2)) were prepared by the reaction of Pd(NCN)() with equi-molar amount of -p-X. Treatment of Pd(NCN)() with an excess amount of -p-Me affords the hydrogen-bonding adduct complex 3 (-p-Me). Complex 3 can also be obtained from benzene solution of 2 in the presence of free -p-Me. Complex 1 does not undergo adduct formation with neither from metathesis reaction of Pd(NCN)() with an excess amount of nor from treatment of 1 with free . Complex 3 undergoes fast exchange of the coordinated p-cresolate with the hydrogen-bonding p-cresol. Complex 2 undergoes -ligand exchange reaction with to give 1. The exchange reaction, however, is irreversible as readily anticipated from their respective values of the phenol derivatives. Reaction of 2 with diphenyliodium chloride quantitatively produced Pd(NCN)Cl and PhI along with liberation of O-phenylated product -p-Me which was identified by GC/MS spectroscopy.