Synthesis and Spectroscopic Characterization of Organothiophosphoryl Polyoxotungstates α‐[RP(S)] 2 PW 9 ${\rm O}^{5-}_{34} $ (R=C 6 H 5 , C 6 H 11 )

In the presence of Bu 4 NBr acting as phasetransfer reagent, organothiophosphoryl polyoxotungstate derivatives α‐[RP(S)] 2 PW 9 ${\rm O}^{5-}_{34} $ (R=C 6 H 5 , C 6 H 11 ) have been obtained by reaction of the trivacant β‐[PW 9 O 34 ] 9‐ anions with electrophilic C 6 H 5 P(S)Cl 2 or C 6 H 11 P(S)Cl 2 in acetonitrile. These new organic‐inorganic hybrid anions have been characterized by elemental analysis, IR, 31 P and 183 W NMR spectroscopy. The collective application of the spectroscopy data of these new species indicates that the hybrid anion consists of an α‐[PW 9 O 34 ] framework on which are grafted two RP(S) groups through P‐O‐W bridges. The five‐line 183 W spectra indicate that the hybrid anions possess C s symmetry in acetonitrile.