Investigation of the reaction of [Cp*2M2O5] (M=Mo, W) with hydrogen peroxide and tert-butylhydroperoxide in MeCN; implications for olefin epoxidation catalyzed by organomolybdenum and organotungsten compounds - Archive ouverte HAL Accéder directement au contenu
Article Dans Une Revue Journal of Organometallic Chemistry Année : 2014

Investigation of the reaction of [Cp*2M2O5] (M=Mo, W) with hydrogen peroxide and tert-butylhydroperoxide in MeCN; implications for olefin epoxidation catalyzed by organomolybdenum and organotungsten compounds

Résumé

Compounds [Cp*2M2O5] (M = Mo, W) react with stoichiometric amounts of H2O2 (as a 30% w/w solution in water) and tBuOOH (TBHP, as a 70% w/w solution in decane) in MeCN solution to yield a variety of products as shown by the 1 H NMR monitoring of the Cp* resonance. The reaction rate increases in the order W < Mo and TBHP < H2O2. While the total Cp* intensity remains constant when using stoichiometric amounts of oxidant, use of excess oxidant results in the ultimate total Cp* loss. From the decomposed solutions, crystals of [Cp*2Mo6O17] (1), (C5Me5O)[Cp*M6O18] (M = Mo, 2a; W, 2b), and (C5Me5O)2[Mo6O19] (3) were recovered and analyzed by X-ray diffraction. Catalytic cyclooctene epoxidation experiments with (nBu4N)2[M6O19] (M = Mo, W) in a 3:1 MeCN/toluene mixture at 55°C using either aqueous H2O2 or TBHP/decane as oxidant revealed that these are not the active forms of the catalyst which is generated under the same conditions from [Cp*2M2O5], as reported in previous contributions from our group (Chem.
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hal-02007933 , version 1 (02-03-2021)

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Chanchal Bhaumik, E. Manoury, Jean-Claude Daran, Pelin Sözen-Aktaş, F. Demirhan, et al.. Investigation of the reaction of [Cp*2M2O5] (M=Mo, W) with hydrogen peroxide and tert-butylhydroperoxide in MeCN; implications for olefin epoxidation catalyzed by organomolybdenum and organotungsten compounds. Journal of Organometallic Chemistry, 2014, 760, pp.115-123. ⟨10.1016/j.jorganchem.2013.11.029⟩. ⟨hal-02007933⟩
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