Abstract: | Complex Formation of N-(Thiocarbamoyl) benzamidines N-(Thiocarbamoyl)benzamidines 1 and N-(Thiocarbamoyl)-N′-phenyl-benzamidines 2 form in alcoholic solutions with Ni2+, Cu2+, Pd2+, Co3+, and Ag+ ions well crystallized chelates 1a ? h and 2a? h , respectively, with N/S coordination. The X-ray photoelectron spectra evidence the NH group as ligator in the case of chelates of 1 and the increased donor capacity compared with the isosteric oxygen ligator atom bound to nickel. This is confirmed by d-1H-n.m.r. spectroscopy analyzing the value of ΔGc≠ for the rotational barrier for the Et2N group of 1a |