Metal cations (Cu(II), Fe(III), Mn(II), and Ni(II)) are ligated by amaranthus starch as proven by EPR spectra and conductivity measurements. The hydroxyl groups of starch are the coordination sites. The acetate and nitrate anions of the metal salts behave as bidentate ligands and reside in the inner coordination sphere of resulting polycenter Werner complexes. There is only a weak degeneration of orbitals of central metal ions caused by a shift of unpaired spin from the central atom to the ligand. The ligation of the central metal atoms resulted in a variation of the thermal stability, pathway, and rate of thermal decomposition of starch as proven by thermogravimetric (TG) and differential scanning calorimetric (DSC) measurements. (C) 2002 Elsevier Science B.V. All rights reserved.