关键词: 一缺位杂多阴离子, 有机膦, 合成, NMR(³¹P, ¹⁸³W)

Abstract: With Bu₄NBr as phase-transfer agent, the monovacant polyoxometalates α-Xⁿ⁺W₁₁O₃₉^(12-n)-(X=P, Si, B, Ga) reacted in acetonitrile with electrophilic C₆H₅P(S)Cl₂ to yield hybrid organic-inorganic species [C₆H₅P(S)]₂XW₁₁O₃₉^(8-n)- in satisfactory yield, which have been characterized by elemental analyses, IR and ³¹P, ¹⁸³W NMR. The formulation of all tetrabutylammonium salts of [C₆H₅P(S)]₂·XW₁₁O₃₉^(8-n)- are in agreement with the results of elemental analyses, the hybrid anion consists of an α-Xⁿ⁺W₁₁O₃₉^(12-n)- framework on which are grafted two C₆H₅P(S) groups through P—O—W bridges. The spectroscopic data show that the [PhP(S)]₂XW₁₁O₃₉^(8-n)- compounds possess true C_s symmetry in acetonitrile and remain unsaturated.

Key words: Monovacant heteropolyanion, Organophosphorus, Synthesis, NMR(³¹P,¹⁸³W)