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Hexanuclear complexes of molybdenum(V) containing [Mo_6O_1_2(OCH_3)_4(acac)_3]^- anion

The novel hexanuclear oxoclusters of the general formula R[Mo_6O_1_2(OCH_3)_4(acac)_3] (1-7), where R = CH_3NH_3 (1), C_5H_5NH (2), (CH_3)_2CHNH_3 (3), (CH_3)_3CNH_3 (4), C_5H_1_1NH (5), (C_2H_5)_3NH (6), and C_6H_5NC_1_1H_1_3O_2 (7) have been obtained by the reactions of the binuclear oxomolybdenum(V) complex [Mo_2O_3(acac)_4] (acac = acetylacetonate ion) with variety of alkyl or aryl amines or corresponding alkyl or aryl ammonium chlorides in methanol. The formation of 3, 5-diacyl-2, 6-dimethyl-1-pheny-l-pyridinium cation in 7 is explained by the cyclization via Hantzsch condensation of acetylacetone, formaldehyde and aniline. The molecular structures of complexes 5, 6 and 7 have been determined by a single-crystal X-ray diffraction study. In all salts the anion is of hexanuclear nature in which molybdenum atoms are bridged by oxo-oxygen and methoxo-oxygen atoms. Six Mo-octahedra are fused through edges, thus allowing the formation of localized metal - metal bonds between tree pairs of molybdenum atoms.

molybdenum; oxocluster complexes; Hantzsch synthesis; crystal structures; hexanuclear molybdenum(V) complexes

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