0000000000299395
AUTHOR
Funda Demirhan
High oxidation state aqueous organometallics: synthesis and structure of a dinuclear oxo(pentamethylcyclopentadienyl)acetato complex of molybdenum(IV), [Cp*Mo(μ-O)(μ-O2CCH3)]2
International audience; The zinc reduction of Cp*2Mo2O5 in a MeOH–H2O mixture in the presence of acetic acid affords the diamagnetic dinuclear compound [Cp*MoO(O2CCH3)]2. An X-ray structural investigation reveals a novel dioxo- and diacetato-bridged structure, with a relatively strong metal–metal bond [2.5524(3) Å]. The compound exhibits a reversible one-electron oxidation process in the cyclic voltammogram. A comparison with other related structures reveals the effect of the electric charge on the mononuclear or dinuclear structural choice.Zinc reduction of Cp*2Mo2O5 in water–methanol in the presence of acetic acid affords compound Cp*2Mo2O2(O2CCH3)2, whose dinuclar tetrabridged structure …
Cyclopentadienylmolybdenum(VI) and molybdenum(V) oxo chemistry: New synthetic and structural features
International audience; Convenient syntheses for Cp, Cp*, and related cyclopentadienyl derivatives (4Cp = C5HiPr4; Cp′′′ = C5H2tBu3-1,2,4) of formula [(Ring)2Mo2O5] are described. Compound [Cp2Mo2O5] was produced in good yields by the rapid oxidation of red [CpMoO2]4 with PhIO in CH2Cl2. [Cp*2Mo2O5] was obtained by CH3COOH acidification of aqueous solutions of [Cp*MoO3]−Na+, the latter being generated in a single step from [Cp*MoCl4] and more than 5 equiv. of aqueous NaOH in air. Minor quantities of [Cp*MoO2]2 were also isolated from this reaction, although the formation of this by-product may be reduced by using a two-step basic hydrolysis procedure. Extension of the latter strategy also a…
High oxidation state aqueous organometallics. Formation and structure of an oxo-centred Cp*MoV trinuclear cation by chemical reduction of Cp*2Mo2O5
International audience; Reduction of Cp*2Mo2O5 by zinc/CF3CO2H in MeOH–H2O yields a salt which is composed of [Cp*3Mo3O4(O2CCF3)3]+ and [Zn2(O2CCF3)6]2− ions after crystallisation from THF–Et2O.