Structural organization of mercury(II) and copper(II) dithiocarbamates from EPR and 13C and 15N MAS NMR spectra and X-ray diffraction analysis

Autor: Alexander S. Goryan, Oleg N. Antzutkin, B. V. Bukvetskii, E. V. Korneeva, Willis Forsling, Alexander Ivanov
Rok vydání: 2008
Předmět:
Zdroj: Russian Journal of Coordination Chemistry. 34:59-69
ISSN: 1608-3318
1070-3284
DOI: 10.1134/s1070328408010107
Popis: The structures and spectroscopic properties of mononuclear and binuclear mercury(II) and copper(II) complexes with four dithiocarbamate ligands R2NC(S)S− (R = CH3, C2H5, or iso-C3H7; R2 = (CH2)6) were studied by solid-state 13C and 15N CP/MAS NMR and EPR spectroscopy. Mercury(II) N,N-cyclohexamethylenedithiocarbamate [Hg2{S2CN(CH2)6}4] was obtained and characterized in detail by X-ray diffraction analysis at 299 K. The binuclear molecule of the complex is centrosymmetric; the central tricyclic fragment [Hg2S4C2] is in the chair conformation. In the 13C and 15N NMR spectra, the signals were assigned to the dithiocarbamate ligands with different structural functions: bidentate chelating and combined (both chelating and bridging) ones. The differences between the isotropic 15N chemical shifts for the dialkyldithiocarbamate ligands were interpreted in terms of combination of the mesomeric effect of the =NC(S)S-groups and the inductive effect of the alkyl substituents. According to the EPR data, copper(II) in magnetically diluted systems is mainly found in heterobinuclear molecules [CuHg(S2CNR2)4] and the geometry of the chromophores [CuS5] approximates to a tetragonal pyramid.
Databáze: OpenAIRE
Externí odkaz: