Synthesis and characterization of an N-coordinated amidate copper(II) complex of deprotonated N-(2,6-diisopropylphenyl)-2-(bis-(2-pyridylmethyl))aminoethanamide

The title ligand, N-(2,6-diisopropylphenyl)-2-(bis-(2-pyridylmethyl))aminoethanamide (DIPMAE-H), was prepared by a nucleophilic substitution reaction between N-(2,6-diisopropyl)phenyl-2-bromoethanamide and bis-(2-pyridylmethyl)amine. An analogous ligand (TBPMAE-H) in which the 2,6-diisopropylphenyl group was substituted for a tert-butyl group was also prepared in this manner. Then, [(DIPMAE-H)CuBr]+Br− and [(TBPMAE-H)CuBr]+Br− were prepared by heating one equivalent of ligand and CuBr2 in CH3CN. In both compounds the geometry about the copper center is square pyramidal with distortions due to the geometrical constraints of the ligand. The amide oxygen occupies the axial position, and the three amine nitrogens and the bromide ligand form the basal plane of the square pyramid. Pairs of complexes in the unit cell are associated via weak donation of a lone pair on the bromide ligand of one complex to the copper center of another (Cu⋯Br distances in the range of 3.3576–3.4022 Å).The title compound, (DIPMAE)CuBr, was prepared by deprotonation of [(DIPMAE-H)CuBr]+Br− using NaH. The key feature of (DIPMAE)CuBr is the amidate group η1- and N-coordinated to the copper center. The compound also exhibits distorted trigonal bipyramidal coordination geometry with the bromide and tertiary amine donors occupying the axial sites and the amidate and pyridyl donors occupying the equatorial positions. The copper atom is displaced from the trigonal plane towards the bromide donor apex due to the geometrical demands of the ligand.

The title compound, CuBr(C26H31N4O), was readily synthesized by deprotonation of a precursor complex, CuBr2(C26H32N4O), formed from CuBr2 and N-(2,6-diisopropylphenyl)-2-(bis-(2-pyridylmethyl))aminoethanamide. The title compound exhibits distorted trigonal bipyramidal coordination geometry with the bromide and tertiary amine donors occupying the axial sites and the amidate and pyridyl donors occupying the equatorial positions. The key feature of the compound is the amidate group η1- and N-coordinated to the copper center.Figure optionsDownload as PowerPoint slide