Syntheses and Structures of a Class of Bridged Bis(Amidinate)s and Derivatives

Abstract

A series of different types of ‘bridge’ linked bis(amidinate)s have been prepared. Reactions of a variety of linked diamines with pivaloyl chloride yielded the corresponding diamides in very high yields. Conversion of the diamides to the diimine chloride is achieved with PCl₅ in CH₂Cl₂. Reactions of the diimine chloride with aniline or t-butyl amine yielded the bis(amidinate)s in good yields, while reaction with pyrrolyl sodium or 2,5-dimethyl pyrrolyl potassium afforded the corresponding derivatives. Their structures were characterised by NMR and HRMS, and some products were further characterised by X-ray crystal structure analysis. It was found that the locations of the hydrogen atoms within the two amidine fragments vary. The structures showed that in the phenylene-linked bis(amidinate)s, the hydrogen atoms were attached to different nitrogen atoms in the amidine groups, and in the cyclohexylene-linked bis(amidinate)s or their derivatives, the C=N of the amidine groups were conjugated with the aromatic rings.