Abstract The peculiarities of the 35Cl, 79Br NQR spectra of the chalcogenhalide complexes are explained in terms of intraspheric effect of ligands, formation of secondary intra-and intermolecular bonds, and electronic structure of metal atom. In the 35Cl spectra of [TeCl3 ]2[OsCl6 ] 1, [SeCl3]2[OsCl6]2 and [TeCl3]2 [ReCl6 ]3 the 7-10% increase in frequency in the low-frequency multiplet are accounted for by the disturbance of the pHal-dM π-interaction due to the formation of the peripheral coordination polyhedra [SeCl6 ] and [TeCl6 ]. The peculiarities of the 35 Cl and 79 Br spectra of [MoS2 Cl3 (SeCl2)]2 4, [MoS2 Br3 (SeCl2)]2 5, [WS2Cl3 (SeCl2)]2 6 and [WS2 Br3 (SeBr 2)] 2 7 are attributed to the disturbance of the pHal-dM π-interaction under the influence of the coordination of the SeCl2 and SeBr2 ligands and formation of secondary intramolecular bonds. For [RhCl3 (SeCl2)2]2 8, [IrCl3 (SeCl2)2]2 9 and [SCl3 ][IrCl4 (SCl2)2]10, the appearance of frequencies at 25 MHz in low-frequency triplets is attributed to the intraspheric effect of weak donors-neutral SCl2 and SeCl2 molecules; the frequencies at 18 MHz are assigned to bridging chlorine atoms. This assignment was confirmed by the dimeric structure, which was established by an X-ray structure analysis.