, Volume 3, Issue 1-3, pp 79-91

Functionalization of polyoxomolybdates: the example of nitrosyl derivatives

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Nitrosyl derivatives of polyoxomolybdates have been synthesized and characterized by X-ray diffraction. Most of them contain the MoII(NO)3+ unit and their structures are related to the following structural types: Lindqvist, Keggin and decatungstate [W10O32]4−. Reductive nitrosylation of (NBu4)4[α-Mo8O26] by hydroxylamine in methanol yields (NBu4)2[Mo5O13(OMe)4(NO){Na(MeOH)}]. 3MeOH, which is a versatile reagent yielding a variety of derivatives (i) by the transformation of [Mo5O13(OMe)4(NO)]3− into [Mo6O18(NO)]3− in acetonitrile, (ii) by the formation of [PMo12O39(NO)]4− by reaction of [Mo5O13(OMe)4(NO)]3− with [PMO12O40]3− in basic condition and (iii) by the formation of mixed valence MoVI/MoV/MoII decamolybdates [Mo10O24(OMe)7(NO)]2−, [Mo10O25(OMe)6(NO)] and [Mo10O20(OMe)9(NO)3]2− by chemical reduction of [Mo5O13(OMe)4(NO)]3−; MoII is localized while MoV are delocalized in the first two species but localized in the third. The unique ligating properties of [Mo5O13(OMe)4(NO)]3− have been documented: this species acts as a tetradentate ligand in [Ce{Mo5O13(OMe)4(NO)}2]2−, a symmetrically tetraligating ligand in [Rh2Cp*2(μ-Br){μ-Mo5O13(OMe)4(NO)}] and a bidentate ligand in [Mo5O13(OMe)4(NO){RhCp*(H2O)}]. Some polyoxomolybdates of the type [Mo5(NO)2O12{RC(NH2)NHO}2{RC(NH)NO}2]2−, which contain the Mo0(NO) 2 2+ unit, have also been characterized.