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Additional info for Chemistry of Iodine in Reactor Safety (Summary, Conclusions) (csni-r1996-07)
Dibromo-o-xylene, the second mercaptide and halide are oriented such that the cyclization reaction proceeds rapidly. This control of the steric course of the reaction by the metal ion is the basis for the kinetic template effect. Many 20 Gordon A. Melson Br macrocycle formation reactions involve condensations between amines and carbonyl-containing compounds. The anticipated synthesis of tetraaza macrocycles that may serve as models for biological molecules has provided much of the impetus to research in this area.
Tris(ethylenediamine)nickel(lI) perchlorate reacts very slowly with Gordon A. Melson 40 Scheme 1 methyl ethyl ketone to give the complex of Me2Et44,14-dieneN4, the "cis imine" isomer of 29. Other nickel(II) and some cobalt(III) complexes of 29 and nickel(II) complexes of the cis isomer have been synthesized, their PMR spectra studied, and isomerism discussed. (140) The reactions of bisligand complexes of nickel(II) containing a variety of diamines with diacetone alcohol have been described.
109) The complexes containing the 14-membered macrocyclic ligands are extremely resistant to chemical attack, being unaffected by boiling acid or basic solutions, or by ammoniacal dimethylglyoxime or sulfide, whereas the nickel(II) complex with the 15-membered ligand is slowly attacked and the complex with the 16-membered ligand is rapidly attacked. Attempts to prepare the copper(II) complex of MesdieneN, were not successful. MacDermott and Busch(l10) showed that, under various conditions, mesityl oxide, diacetone alcohol, and acetone all react with tris(ethylenediamine)nickel(II) salts to yield complexes containing either Mes4,II-dieneN, or the nonmacrocyclic tetradentate ligand 1,9-diamino4,6,6-trimethyl-3,7-diazanona-3-ene.