Polycrystalline and surface O,O '-dialkyldithiophosphate zinc(II) complexes: preparation, P-31 CP/MAS NMR and single-crystal X-ray diffraction studies

Dithiophosphate zinc(II) complexes with eight different O,O'-dialkyldithiop hosphate ligands have been prepared in solid/liquid states and as surface c omplexes on a synthetic sphalerite, and studied by means of P-31 NMR spectr oscopy. All P-31 resonances, corresponding to dithiophosphate ligands with different structural functions (i.e. terminal chelating or bridging between two metal atoms in bi- and tetranuclear complexes), have been assigned on the basis of comparative analyses of chemical shift data for solid complexe s, their melts and chloroform solutions at various concentrations. The brid ging coordination of O,O'-dialkyldithiophosphate ligands by the two neighbo uring zinc(II) atoms was established in the case of zinc(II) complexes form ed at the surface of the synthetic sphalerite. In addition, novel molecular and crystal structures of the binuclear O,O'-di-cyclo-hexyldithiophosphate zinc(II) complex have been resolved by single-crystal X-ray diffraction da ta analysis, and useful correlations with P-31 NMR data for this complex we re obtained. (C) 2001 Elsevier Science B.V. All rights reserved.