Studies of Nickel(II) and Copper(II) Complexes with Some Aminoalcohols, β-Aminoketones and β-Aminoimines

Abstract

The preparations and properties of some β-aminoimine complexes are described. complexes were formed by reaction of 4-amino-4-methylpentan-2-one with nickel (II) complexes of ethane-1,2-diamine, propane-1,2-diamine,3-azapentan-l,5-diamine, 3-azahexane-1,6-diarmine, 4-azaheptane-l, 7-dianine, 2-aminoethylpiperazine, 3,6-diazaoctane-l,8-diamine and 2-aminoethanol. Some di- and tetranuclear copper(II) compounds were formed by reaction of 4-amino (or 4-hydroxy)-4-methylpentan-2-one with copper(II) complexes of 2-aminoethanol or 3-aminopropanol and by reaction of copper(II) with 4-amino-4-methylpentan-2-one oxime. The compounds formed from 2-aminoethanol were tetranuclear and showed no spin-spin coupling over 100-300 K, while those formed from 3-aminopropan-l-ol were highly spin-spin coupled and in some cases diamagnetic. For the oxime a dinuclear highly spin-spin coupled complex was formed as well as a bis salt which showed normal susceptibility; a third compound whose structure remained speculative which, from susceptibility measurements, showed the presence of non-coupled and spin-spin coupled copper(II). A novel preparation of quaternary hexamine salts by reaction of ammonia on solutions of formaldehyde and amines neutralised with halo or perchloric acids, and preparation of copper(II) complexes by the base hydrolysis of quaternary hexamine salts formed from 2-aminoethanol and 3-amino-propan-l-ol are also described. The complexes have an unusual bicyclic chelate ligand and are dinuclear. Again the 2-aminoethanol derivatives show only weak spin-spin coupling while the 3-aminopropanol derivative is highly spin-spin coupled. A third section describes the formation of a new β-aminoketone ammonium salt, 4,4,12,l2-tetramethyl-5,8,11-triazapentadeca-2,14-dione dihydroperchlorate by reaction of 3-azapentane-l,5-diamine with acetone and discusses formation and properties of cobalt(II), copper(II) and nickel(II) complexes of this ligand. Nickel(II) and copper(II) complexes of reductive cyclization product, 4,4-dimethyl-7-(5,5,7-trimethylperhydro-1,4-diazepine-l-yl)-5-azaheptan-2-ol, formed by sodium borohydride reaction with the β-aminoketone ammonium salt are described.