Alcohol-soluble functional vic-dioxime bearing alcoholhexylsulfanyl moieties: preparation, spectroscopy and electrochemistry

Abstract

A new alcohol soluble functionalized vic-dioxime, bis-[(1-hydroxyhexyl)-(8,9-hydroxyimino)-7,10-dithiahexacosane (LH2), and its alcohol-soluble mono and dinuclear complexes (Ni-II, Cu-II, Co-II, Mn-II, Pd-II and UO2II) have been prepared from 6-mercapto-1-hexanol and (E,E)-dichloroglyoxime under high dilution basic conditions. Reactive polyalcohol moieties appended at the periphery of the oxime containing two different heteroatoms (S-, O-), serve as a weak exocyclic binding sites for Pd (II) and Ag (I) metal ions and also provide solubility for the vic-dioxime complexes in low molecular-weight alcohols. Both mono-nuclear (LH)(2)M and homodinuclear (LH)(2)(UO2)(2)(OH)(2) and heterotrinuclear (LH)(2)MM(2)(')Xn, where M = Co-II M' = Pd-II, X = Cl-, n = 4 and Ag-I X = NO3-, n = 2) complexes have been obtained with a 1:2, 2:2, 3:2 metal/ligand ratio, respectively. Electronic spectra of the modified vic-dioximes exhibit monitorable changes in UV. All mono and dinuclear-complexes are soluble in common organic solvents. The elemental analysis, H-1-n.m.r, i.r., u.v-vis, and f.a.b.-m.s data and by cyclic and differential pulse voltammetry measurements are presented.