0000000000437518
AUTHOR
Dirk Saurenz
Improved Preparations of Molybdenum Coordination Compounds from Tetrachlorobis(diethyl ether)molybdenum(IV)
International audience; The reduction of MoCl5 with metallic tin in diethyl ether provides a rapid and convenient entry to [MoCl4(OEt2)2] This compound can be transformed easily and in high yields into a variety of other useful synthons. The loss of ether in the solid state affords a new and reactive form of MoCl4. Treatment with THF, PMe3 or LiOtBu affords [MoCl4(THF)2], [MoCl4(PMe3)3] or [Mo(OtBu)4] in high isolated yields. Treatment with metallic tin in THF affords [MoCl3(THF)3] All of these reactions can be carried out under simple experimental conditions and represent significant improvements relative to previously reported syntheses of the same compounds.
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…
Studies on the Reduction of [(C 5 Me 5 ) 2 Mo 2 O 5 ] in Methanol/Water/Acetate Solutions by On‐Line Electrochemical Flowcell and Electrospray Mass Spectrometry
The complex [Cp*2Mo2O5] (Cp* = η5-C5Me5) and its electrochemical reduction products in acetic acid/acetate-buffered (pH = 4.0) water/methanol solutions were investigated by combined electrochemical (EC) flowcell and on-line electrospray ionization mass spectrometry (ESI-MS). Mono-, di-, tri-, and tetranuclear organometallic molybdenum oxides were identified in the starting solution. The effect of the relevant ESI-MS parameters (ionic mode, heated capillary voltage, and heated capillary temperature) and of the concentration on the observed distribution of ions in the mass spectrometer was studied in order to minimize side reactions in the ESI chamber. It was verified that reduction in the ES…