Heteronuclear NMR spectroscopy is used by us to study the stereochemistry and stereodynamics of coordination compounds; it allows one to determine the structure of cistrans-isomers of tetrahedral and octahedral metal complexes and the ability of bi- and polynuclear ligands to react with metal ions by different nucleophilic donor centers. The method of localizing coordination bond by heteronuclear NMR spectroscopy is determined by comparing NMR spectral tests of the characteristic fragments of potential polydentate ligands and coordination compounds, full correlation of spectroscopic data with X-ray of the key compounds being observed. The main objects of our investigation are coordination compounds of Cu+ , Ni2+, Zn2+ , Ru2+, Rh3+, Pd2+, Pt2+ ions with carbothioamide derivatives. The following changes in the chemical shift of signals in 1H, 13C NMR spectra at complex formation have been established:  The most characteristic chemical shifts (ΔС8=-15.03, ΔС2=-8.92, ΔС7=-6.7 ppm) are observed for the 13C nuclei located near the coordination center. In contrast to 1H NMR, the direction of change in chemical shift (to upfield or down magnetic field) in 13C NMR spectra is independent of the nature of complexing agent.  In 1H NMR spectra, the most characteristic chemical shifts to strong field are observed for the protons located at nucleophilic donor centers, which are involved in complex formation (ΔН3=-0.525, ΔН7=-0.138 ppm), the rest protons of the aromatic nucleus shifting to weak field, ΔН=0.048-0.148 ppm. Two- dimensional 1Н1Н, 1Н13С NMR spectroscopy using the procedures COSY, НMQC, HMBC, NOESY was employed for the complete assignment of signals [1-2]. It should be noted that a fairly informative methods for determining the oxidation of the metal and form of coordinated ligands in the complexes is X-ray photoelectron spectroscopy (XPS). This is one of the main methods of investigation of chemical bond in compounds. It allows studying the valence and inner electron levels of atoms. It has been shown that increase in the S2p3/2 electron binding energy in the spectra of complexes (ΔEbind.S2p 0.6-1.3 eV) characterizes the coordination ligand in thionic tautomer form. At the same time, coordination of ligand to metal trough the azomethine nitrogen atom on the donor-acceptor mechanism causes a shift of Ebind.N1s (ΔEbind.N1s 0.6-1.1 eV), whereas bond formation (NH→M) hardly causes a shift of N1s binding energy, which characterizes the weak donoracceptor interaction between the protonated nitrogen atoms and the metal ion. It has been determined the location of chloride ions in the inner (finite and bridge position) and outer coordination sphere of complexes. The positions of Rh3d5/2 and Pd3d5/2 signals at 311.1 eV and 339.0 eV are assigned to tri- and bi-valent states of the metal ions. It is shown that the metal coordination polyhedron formed by nitrogen, sulfur, oxygen, chlorine atoms, and/or water molecules [3].