Peculiarities of the 35C1 and 79Br NQR Spectra of Chalcogenhalide Complexes of Some Transition Metals.
Ministry of Education and Science of Ukraine
Department of Chemistry
The peculiarities of the 35C1, 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 35C1 spectra of [TeCl3]2[OsCl6] 1, [SeCl3]2[OsCl6]2 and [reCl3]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 35C1 and 79Br spectra of [MoS2Cl3(SeCl2)]24, [MoS2Br3(SeCl2)]25, [WS2Cl3(SeCl2)]26 and [WS2Br3(SeBr2)]27 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]28, [IrCl3(SeCl2)2]29 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 SC12 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.
Fokina, Z. A.; Kolesnichenko, Vladimir; Pekhnyo, V. I.; and Volkov, S. V., "Peculiarities of the 35C1 and 79Br NQR Spectra of Chalcogenhalide Complexes of Some Transition Metals." (1997). Faculty and Staff Publications. 104.