
%0 Journal Article
%A Curtis, NF 
%T Complexes of Nickel(II) and Copper(II) With 5,5,7-Trimethyl-1,4-Diazepane. Preparation and Kinetics of Acid-Hydrolysis
%J Australian Journal of Chemistry
%D 1986/02/01
%V 39
%N 2
%P 239-247
%K 
%R https://doi.org/10.1071/CH9860239
%U https://www.publish.csiro.au/paper/CH9860239 
%X The cyclic diamine 5,5,7-trimethyl-1,4-diazepane, tmdz, is formed by borohydride reduction of 5,7,7-trimethyl-2,3,6,7-tetrahydro-1H-1,4- diazepine , which is formed by a rapid reaction between ethanediamine and 4-methylpent-3-en-2-one. Salts of the cations [Ni( tmdz )2]2+ and [Cu( tmdz )2]2+ were prepared, and their properties are reported. The kinetics of hydrolysis of [Ni( tmdz )2]2+ and [Cu( tmdz )2]2+ and bis (1,4- diazepane )nickel(II), [Ni( dach )2]2+, in aqueous HCl/NaCl media have been studied. Reaction rates are independent of acid concentration over the ranges used . Ni2+,0.1-1 mol l-1 H+ in 1 mol l-1 Cl -, kobs(25&#176;C) = 9.1(1)&#215;10-7 s-1, kobs(50&#176;C) = 2.0(1)&#215;10-5 s-1,&#916;H&#8225;96(2)kJ mol-1,0.08-4 mol l-1, H+ in 4 mol l-1 Cl -, kobs (25&#176;pC) = 2.0(3)&#176;10-7 s-1. Cu2+, 0.04-1 mol l-1 H+, 1 mol l-1 Cl -, kobs (25&#176;C) = 0.028(2) s-1, for the displacement of the second ligand . [Ni( dach )2]2+, 0.1-1 mol l-1 H+, 1 mol l-1 Cl -, kobs (25&#176;C) = 0.051(2) s-1. [Ni( tmdz )2]2+ reacts more rapidly with NaOH/edta : 1 mol l-1 NaOH , 0.1 mol l-1, Na2(edtaH2), kobs (25&#176;C) = 7.3(3)&#215;10-3 s-1, 0.5 mol l-1 NaOH , 0.1 mol l-1 Na2(edtaH2), kobs (25&#176;C) = 4.5(3)&#215;10-3 s-1. 
