Polymeric thallium(I) O,O'-diisopropyl dithiophosphate [Tl{S2P(O-iso-C3H7)2}] n : Synthesis, structure, and 13C and 31P CP/MAS NMR spectra

The crystalline polymeric thallium(I) O,O'-diisopropyl dithiophosphate [Tl{S2P(O-iso-C3H7)(2)}] (n) (I) was obtained and examined by solid-state C-13 and P-31 CP/MAS NMR spectroscopy. Diagrams of the chi(2) statistic were constructed from the complete P-31 MAS NMR spectra and used to calculate the P-31 chemical shift anisotropy (delta(aniso) = (delta (zz) - delta(iso))) and the asymmetry parameter (eta = (delta (yy) - delta (xx) )/(delta (zz) - delta(iso))). The P-31 chemical shift tensor has a nearly axial symmetry (eta = 0.22, delta (zz) < delta (yy) a parts per thousand delta (xx) ). The MAS NMR spectral patterns correspond to the negative sign of delta(aniso) (delta (zz) < delta (yy) < delta (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-mu(3)-bridging fashion. The shape of the P-31 NMR signal was interpreted in terms of the P-31-Tl-203,Tl-205 coupling pattern proposed from crystallographic data.