Affiliation:
1. Institute of General and Inorganic Chemistry, 32-34 Pr. Palladina, Kiev-142,252680, Ukraine
2. Institute of Organoelement Compounds. 28 Vavilova St. Moscow, Russia
Abstract
The 35C1 NQR spectra of the chlorochalcogenide complexes of iridium (SCl3)2 [IrCl6] 1, (TeCl3)2 [IrCl6] 2, (SeCl3) [IrCl6] 3, [IrCl3(SCl2)2]2 4, (SCl3) [IrCl4(SCl2)2] 5 and [IrCl3(SeCl2)2]2 6 have been studied. The spectra were recorded by pulse spectrometry. They consist of two mul tiplets, widely separated in frequency. The high-frequency multiplet belongs to the chlorine atoms bonded to sulfur, selenium and tellurium, respectively, in the ligand. A high-frequency shift is observed, which is typical for the coordination of the molecules ACl2(A=S, Se) and ACl4(A=S, Se, Te). The low frequencies in the multiplets of 4 and 6 are attributed to additional bonds formed between chalcogen atom and chlorine in the coordination environment of iridium.
In the spectral region 18-24 MHz lie the NQR frequencies of 35Cl bonded to iridium. For 2 the frequencies are close to those of [IrCl6]2-, which confirms the Ir oxidation state IV. The unexpectedly high frequencies for IrIII in the case of 4 and 5 are explained by the influence of ACl2 molecules, which are weaker σ-donors than the chloro ligands. This promotes electron density transfer from neighbouring chlorine atoms. The 18 MHz frequency is assigned to the bridge chlorine atoms in dimeric molecule 4. This assignment is confirmed by the positive value of d v/dT = +0,2.
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