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|Title:||Macrocyclic metal complexes: Part XV-Binuclear nickel (II) macrocyclic ( comlexes, synthesis, structure and electron transfer reactions|
|Authors:||Patra, N C|
Rout, A K
|Abstract:||Dimeric bis-(dibydrazinophthalazine)nickel(II) ion undergoes Curtis type reaction with 2,2-dimethoxypropane in the mole ratios 1:1 and 1:2 yielding binuclear complexes of the type Ni2(daph)X4.nH2O and macrocycles of the type Ni2(taph)X4.nH2O[X = Cl-, ClO, n =4];daph and taph are the abbreviated names of the ligands 4-[2-(4-hydrazino-1-phthalazinylrhydrazino]-4-methyl-2-pentanone(4-hydrazino -1- phthalazinyl)-hydrazone and 8,10,10,19,21,21-hexamethyl-l,3,4,6,7,1l,12,14,15,17,18,22- dodecaazacyclodocosa-2,5:13, 16-bis(phthalazino)-2,4,7,13,15,18-hexaene respectively. These complexes react with sodium borohydride in methanol medium when the imine groups are selectively reduced with uptake of two and four hydrogen atoms respectively [(daph+ 2H) and (taph + 4H)].The reduced ligands are observed to be stronger donors. The complexes of dhph and daph and the macrocycles of taph are electrochemically reduced in two successive steps. On the other hand, the (daph + 2H) and (taph + 4H) complexesundergo two-electron one-step reduction. The convergence of successive redox processes arises from a lower degree of unsaturation in the ligand structure of the second type of complexes that diminishes the tendency for the generation of ligand anion radical.|
|Appears in Collections:||IJC-A Vol.28A(11) [November 1989]|
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