Structural Organization of Silver(I)Complexes with O,O'-Dialkyl Dithiophosphates:Solid-State ~(13)C and ~(31)P CP/MAS NMR and Single-Crystal X-Ray Diffraction Studies

摘要

Silver(I)complexes with four symmetrically substituted 0,0'-dialkyl derivatives of dithiophospho-ric acid of the general formula [Ag{S2P(OR)2}]_n(R = C2H5,i-C3H7,C4H9,and s-C4H9)were obtained.Then-structures and spectroscopic characteristics were studied by solid-state ~(13)C and ~(31)P CP/MAS NMR spectroscopy and X-ray diffraction analysis.The parameters of the anisotropy of the ~(31)P chemical shift ~(31)P-delta_(aniso)and eta(delta_(aniso)is the chemical shift anisotropy and eta is the asymmetry parameter)calculated from the diagrams of the lambda~2-statistic revealed that the(RO)2PS2 groups act as bridging ligands in all the silver(I)complexes obtained.The hexanuclear complex [Ag6{S2P(CM-C3H7)2}6] was found to form two modifications alpha and beta.According to the X-ray diffraction data,the silver(I)complex with O,O'-di-s-butyl dithiophosphate exists as discrete hexanuclear molecules [Ag6{S2P(O-s-C4H9)2}6].In the ~(31)P NMR spectra of P-[Ag6{S2P(O-i-C3H7)2}6],the signals for the phosphorus atoms were assigned to their positions determined from the X-ray diffraction data.