Synthesis and Reaction of Novel (Tetraaza[14]Annulene)Nickel(II) Complexes with Amino Groups in Their Side Chains

Abstract

The replacement reaction of a (tetraaza[l4]annulene)nickel(II) (1) with 3- and/or 4-nitrobenzoyl chlorides led to the corresponding 7,16-dibenzoylated products (2m, 2p). (7,16-Bis(3-aminobenzoyl)tetraaza[14]annulene)nickel(II) (3m) and (7,16-bis(4-aminobenzoyl)tetraaza[14]annulene)nickel(II) (3p) were prepared by hydrogenation of the corresponding dinitro-analogues (2m, 2p). The reaction of 3m with pivaloyl chloride, nicotinoyl chloride hydrochloride and/or isonicotinoyl chloride hydrochloride gave the corresponding amido products (4, 5 g , 5 n ). Methylation of pyridine comprised in 5 g using iodomethane afforded the corresponding dimethylated product (6 g ). The strapped tetraaza[14]annulene nickel(II) (7 g ) was synthesized from 5 g and f , f '-dibromo- m -xylene. These reactions smoothly proceed on the nickel(II) complexes, but do not occur on the metal-free tetraaza[14]annulenes under these conditions except for the nitrobenzoylation.