Synthesis, Structure, and Magnetic Properties of (n-Bu(4)N)(2)[{Ni(MeOH)(2)}(2){Mo(NO)}(2)(&mgr;(3)-OH)(2)(&mgr;-OMe)(4){Mo(5)O(13)(OMe)(4)(NO)}(2)], a New Type of Polyoxometalate Incorporating a Rhomb-like Cluster.
The oxo-nitrosyl compound (n-Bu(4)N)(2)[{Na(MeOH)}Mo(5)O(13)(OMe)(4)(NO)].3MeOH reacts with various nickel(II) salts in methanol to give (n-Bu(4)N)(2)[{Ni(MeOH)(2)}(2){Mo(NO)}(2)(&mgr;(3)-OH)(2)(&mgr;-OMe)(4){Mo(5)O(13)(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 [Mo(5)O(13)(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 {Ni(2)Mo(2)} cluster linked to two terminal [Mo(5)O(13)(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)).
Villanneau
Richard
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Laboratoire de Chimie Inorganique et Matériaux Moléculaires, CNRS ESA 7071, Université Pierre et Marie Curie, 4 Place Jussieu, 75252 Paris Cedex 05, France, and Institut d'Electronique Fondamentale, CNRS UMR 8622, Université Paris-Sud, 91405 Orsay, France.
Proust
Anna
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Robert
Francis
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Veillet
Pierre
P
Gouzerh
Pierre
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