Some nickel(II) beta-amino-ketone and beta-amino-imine compounds; the structures of mer-bis(7-amino-4,4-dimethyl-5-azaheptan-2-one) nickel(II) perchlorate, (2,7,9,9-tetramethyl-3,6,10-triazadodeca-2,6-diene-12-amine)nickel(II) tetrachlorozincate wate

摘要

Reactions of ethane-1,2-diamine compounds of nickel(II) with acetone can yield a variety of products, depending upon conditions. Reaction of [Ni(en)(2)](ClO4)(2) with acetone forms [Ni(amket)(2)](ClO4)(2), which has nickel(II) in octahedral mer-coordination by two tridentate 7-amino-4,4-dimethyl-5-azaheptan-2-one ligands. The secondary amine groups are coordinated trans [Ni-N-mean = 2.104(8) Angstrom, N-Ni-N = 173.1(2)degrees] and the ketone [Ni-O-mean = 2.077(7) Angstrom, O-Ni-O = 86.6(2)degrees] and primary amine [Ni-N-mean = 2.100(8) Angstrom, N-Ni-N = 92.3(2)degrees] groups are coordinated cis. Compounds with the tetradentate ligand 2,7,9,9-tetramethyl-3,6,10-triazadodeca-2,6-diene-12-amine, enacim, which incorporates two diamine and three acetone residues, are formed by the same reactants in the presence of coordinating anions or solvents. The salt [Ni(enacim)][ZnCl4].H2O, formed by refluxing [Ni(en)(3)][ZnCl4] in acetone/methanol, has a square-planar cation, with distances: Ni-N(3) (terminal imine) = 1.894(4), Ni-N(6) (internal imine) = 1.922(4), Ni-N(10) (secondary amine) = 1.912(4) and Ni-N(13) (primary amine) = 1.915(4) Angstrom. The N-isopropylidene imine function of [Ni(enacim)](2+), is slowly hydrolysed to form [Ni(enac)](2+), with the tetradentate ligand 4,6,6-trimethyl-3,7-diazanon-3-ene-1,9-diamine, which incorporates two acetone and two diamine residues. A nitrito compound of this cation, [Ni(enac)(NO2)]ClO4, has two independent but similar cations with the enac ligand in folded coordination with asymmetric O,O'-chelate nitrito ions completing distorted octahedral coordination [mean dimensions: Ni-N-amine = 2.116(4), Ni-N-imine = 2.053(4), Ni-O = 2.113(4) and 2.237(4) Angstrom, O-Ni-O = 57.2(2)degrees]. Preparations of [Ni(enac)(NO2)]ClO4, [Ni(enacim)][ZnCl4].H2O, [Ni(enac)](NCS)(2) and [Ni(enacim)(NCS)(2)] and improved preparations of [Ni(enac)](ClO4)(2) and [Ni(enacim)](ClO4)(2) are reported. (C) 2003 Elsevier B.V. All rights reserved. [References: 30]