title: Reactions of a {Mo16}-type polyoxometalate cluster with electrophiles: a synthetic, theoretical and magnetic investigation.
abstract: A medium-nuclearity mixed-valence polyoxomolybdate [H2Mo16O52]10-={Mo16}(1a) was synthesized using an approach that employed protonated hexamethylenetetramine (HMTAH+) as counter ion and yielded (HMTAH)10 1a.34 H2O (1). The {Mo16} cluster anion exhibits significant nucleophilicity and traps electrophiles such as divalent transition metal ions, resulting in a family of isostructural compounds based on {Mo16M2}-type anions [M(H2O)8H2Mo16O52]6- (M=FeII (2), MnII (3), CoII (4)). The highly reactive nature of the {Mo16} system is also revealed by rearrangement and decomposition reactions of to either slowly form a sodium-bridged heptamolybdate-based chain compound (5) when left in the reaction solution or, in the presence of very high concentrations of electrophiles, to heptamolybdate-based cluster compounds [M2(H2O)9Mo7O24]2- of the {M2Mo7}-type (M=FeII (6), MnII (7)). Compounds were characterised by single crystal X-ray diffraction, elemental analysis, IR spectroscopy, magnetic susceptibility measurements, and density functional theory calculations.
authors.affiliation: Department of Chemistry, The University of Glasgow, Glasgow, UK G12 8QQ.
authors.forename: De-Liang
authors.initials: DL
authors.lastname: Long
authors.forename: Paul
authors.initials: P
authors.lastname: Kögerler
authors.forename: Louis J
authors.initials: LJ
authors.lastname: Farrugia
authors.forename: Leroy
authors.initials: L
authors.lastname: Cronin