Substitutions of coordinated salicylaldehyde and its Schiff bases

Summary Several bis/tris-salicylaldehyde, salicylaldimine and salicyalethylenediimine chelates of cobalt(III), chromium(III), cobalt(II), nickel(II) and copper(II) readily react with various brominating agents and undergo α-bromo/cyano/succinimido substitution, with or without accompanying bromine substitution of the aryl ring. The selectivity of these reactions on the metal-coordinated salicylaldehyde derivatives allows the preparation in 50–80% yield of hitherto unreported specific α-bromo products. The substituted organic compounds could be isolated by demetallation of the chelate products.     

Cobalt(II), nickel(II), copper(II) and zinc(II) complexes of conjugated 3-(benzylidene/salicylidene)-β-diketones (having no enolisable γ-carbon proton) and their reactions

Transition Metal Chemistry - The synthesis and structural characterization of new metal(II) chelates (M = CoII, NiII, CuII and ZnII) of neutral conjugated bidentate β-diketone ligands, having...     

N.m.r. characterisation of linkage isomers

Summary Halogenation of Ln^III, Ce^IV and ZrO^II -diketone/-ketoester derivatives and their mixed ligand complexes of the types Ln(AA)₂(Sal) and Ln(AA)(Sal)₂ by NCS, NBS and PyHBr₃ yield different isomeric products depending on the nature of the solvent medium, the reagent and the reaction time. The halogenation, if carried out in glacial acetic acid, irrespective of the reagent, yields the stable S-hall, product wherein the three chelate rings remain imperturbed in respect of metal coordination. When the reaction is carried out in 5% v/v DMF-CHCl₃ employingN-halosuccinimide and maintaining correct reaction times, it is possible to isolate individually three other isomeric products. The isomers prepared are Ln(OO)₃, Ln(OO)₂(OX), Ln(OO)(OX)₂ and Ln(OX)₃ where (OO) represents diketone oxygen linkage and (OX) represents diketone oxygen and substituted halogen linkage to the central metal ion. The four linkage isomers have been identified by a comparison of the number of observed³H n.m.r. or¹³C n.m.r. signals with those expected for a given isomer on the basis of symmetry considerations in the tris-chelated octahedral structures.     

Cyclic voltammetric and e.s.r. studies of a tetraaza 14-membered macrocyclic copper(II) complex derived from 3-salicylideneacetylacetone ando-phenylenediamine: stabilization and activation of unusual oxidation states

Summary A 14-membered macrocyclic Schiff base derived from 3-salicylideneacetylacetone ando-phenylenediamine acts as a tetradentate and strongly conjugated ligand to form a cationic solid complex with CuCl₂. U.v.-vis. and e.s.r. spectral data reveal a strong ligand to metal -interaction in the square planar complex. C.v. data reveal that the title ligand is able to stabilize the copper(III) oxidation state more effectively than comparable saturated or partially unsaturated macrocyclic ligands and confers a weaker tendency for reduction of copper(II) to copper(I) and copper(0). While the inclusion of a PPh₃ ligand suppresses the Cu⁰ Cu^I Cu^II oxidation, imidazole and pyridine strongly enhance the Cu^II Cu^III oxidation of the complex.