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Organothiophosphoryl polyoxotungstate derivatives α-[C6H11P(S)]2X^n+W11O39^(8-n)-(X=P,Si,Ge,Ga) were obtained by the reactions of the monovacant α-[C6H11P(S)] 2X^n+W11O39^(8-n)-(X=P,Si,Ge,Ga) anions with electrophilic C6H11P(S)Cl2 in acetonitrile. These