
TY  - JOUR
A1  - Curtis, NF 
T1  - Compounds of 3,4,7,9,9,14,16-Octamethyl- (and 7,9,9,14,14,16-Hexamethyl-3,4-diphenyl) 1,2,5,6,10,13-Hexaazacyclohexadeca-2,4,6,16-tetraene With Nickel(II) and Copper(II). Preparations and Kinetics of Acid Hydrolysis Reaction
JF  - Australian Journal of Chemistry
JO  - Aust. J. Chem.
Y1  - 1988
VL  - 41
IS  - 11
SP  - 1665
EP  - 1675
KW  - 
UR  - https://doi.org/10.1071/CH9881665 
N2  - The complex nickel(II) cation of the bis-diazine macrocycle 3,4,7,9,9,14,14,16-octamethyl-1,2,5,6,10,13-hexaazacyclohexadeca-2,4,6,16-tetraene, omht, is formed by reaction of the complex of 3,3,9,9-tetramethyl-5,8-diazadodecane-2,11-dione dihydrazone with butane-2,3-dione, and the complex of the 7,9,9,14,14,16-hexamethyl-3,4-diphenyl homologue, bzht, is similarly prepared by reaction with 1,2- diphenylethane-1,2-dione. The cation [Cu(hmtd)]2+ is formed by metal ion substitution for a precursor of the nickel(II) cation. Compounds of the nickel(II) cations occur as singlet ground state perchlorate salts, or as triplet ground state octahedral compounds with additional ligands, e.g. [Ni(omht)(NCS)2], [{Ni(omht)(N3)}2](ClO4)2 and [Ni(omht)(en)] (ClO4)2. The singlet ground state [Ni(omht)]2+ cation in dimethyl sulfoxide converts into a triplet ground state species with first-order rate constant of 2.1(2)&#215;10-6 s-1 at 25&#176;C, 5.1(2)&#215;10-5 s-1 at 50&#176;C. The cations are slowly hydrolysed by acid, and pseudo-first-order rate constants in 2 mol l-1 HCl/NaCl for hydrolysis of [Ni(omht)]2+ and [Cu(omht)]2+ at 25&#176; and 50&#176;C are reported. These are of the order of 10-5 (25&#176;C), 10-4(50&#176;C) s-1, with a non-linear dependence on [H+], and with the reactions faster for the nickel(II) cation. 
ER  -

