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ABSTRACT: The crystalline polymeric thallium(I) O,O′-diisopropyl dithiophosphate [Tl{S2P(O-iso-C3H7)2}]
n
(I) was obtained and examined by solid-state 13C and 31P CP/MAS NMR spectroscopy. Diagrams of the χ2 statistic were constructed from the complete 31P MAS NMR spectra and used to calculate the 31P chemical shift anisotropy (δaniso = (δ
zz
− δiso)) and the asymmetry parameter (η = (δ
yy
− δ
xx
)/(δ
zz
− δiso)). The 31P chemical shift tensor has a nearly axial symmetry (η = 0.22, δ
zz
< δ
yy
≈ δ
xx
). The MAS NMR spectral patterns correspond to the negative sign of δaniso (δ
zz
< δ
yy
< δ
xx
), which indicates bridging or chelating-bridging coordination of the dithiophosphate ligands (Dtph). X-ray diffraction analysis
revealed a polymeric structure of compound I. The polymer chain consists of alternating mononuclear [Tl{S2P(O-iso-C3H7)2}] molecules with opposite spatial orientations. The Dtph ligands are coordinated in a mixed, chelating-μ3-bridging fashion. The shape of the 31P NMR signal was interpreted in terms of the 31P-203,205Tl coupling pattern proposed from crystallographic data.
Russian Journal of Coordination Chemistry 04/2012; 35(11):857-863. · 0.55 Impact Factor
