Synthesis, Structure, and Magnetic Properties of (<i>n</i>-Bu<sub>4</sub>N)<sub>2</sub>[{Ni(MeOH)<sub>2</sub>}<sub>2</sub>{Mo(NO)}<sub>2</sub>(μ<sub>3</sub>-OH)<sub>2</sub>(μ-OMe)<sub>4</sub>{Mo<sub>5</sub>O<sub>13</sub>(OMe)<sub>4</sub>(NO)}<sub>2</sub>], a New Type of Polyoxometalate Incorporating a Rhomb-like Cluster
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The oxo−nitrosyl compound (n-Bu4N)2[{Na(MeOH)}Mo5O13(OMe)4(NO)]·3MeOH reacts with various nickel(II) salts in methanol to give (n-Bu4N)2[{Ni(MeOH)2}2{Mo(NO)}2(μ3-OH)2(μ-OMe)4{Mo5O13(OMe)4(NO)}2], which has been characterized by single-crystal X-ray diffraction analysis and magnetic susceptibility measurements. This reaction shows the dual behavior of the defect Lindqvist-type species [Mo5O13(OMe)4(NO)]3-, which can act both as a ligand and as a source of the {Mo(NO)}3+ unit. Furthermore, the reaction is reminiscent of the dissolution−precipitation of oxide supports in the preparation of supported catalysts and provides a novel illustration of the potential of polyoxometalates for probing the reactivity of oxides. The new polyoxomolybdate is made of a central rhomb-like {Ni2Mo2} cluster linked to two terminal [Mo5O13(OMe)4(NO)]3- units, each terminal cluster being linked to a molybdenum center of the central unit through two oxo ligands. The two Ni(II) ions are coupled in a ferromagnetic way (J = 13.1 cm-1).
