Oxidation of Thiophene Derivatives with H 2 O 2 in Acetonitrile Catalyzed by [Cp* 2 M 2 O 5 ] (M = Mo, W): A Kinetic Study - Archive ouverte HAL Accéder directement au contenu
Article Dans Une Revue Organometallics Année : 2008

Oxidation of Thiophene Derivatives with H 2 O 2 in Acetonitrile Catalyzed by [Cp* 2 M 2 O 5 ] (M = Mo, W): A Kinetic Study

Résumé

The oxidation of benzothiophene (BT), dibenzothiophene (DBT), and 4,6-dimethyldibenzothiophene (DMDBT) by H2O2 to the corresponding sulfoxides and sulfones has been studied under homogeneous conditions in MeCN with the compounds [Cp*2M2O5] (M = Mo (1), W (2)) as precatalysts. The W system is ca. 100 times more efficient than the Mo analogue, while the relative reactivity of the thiophene substrates is approximately DBT/DMDBT/BT ≈ 10/5/1. For all reactions rate constants for both steps (thiophene derivative to sulfoxide, k1; sulfoxide to sulfone, k2) were measured. While k1 ≈ k2 for DBT and DMDBT, k1 << k2 for BT, independent of catalyst. Activation parameters for the stepwise oxidations of thiophene derivative to sulfoxide (BT to BTO, ΔH⧧ = 11.4(5) kcal mol−1 and ΔS⧧ = –26.1(1.6) eu; DBT to DBTO, ΔH⧧ = 7.7(6) kcal mol−1 and ΔS⧧ = –33(2) eu) and sulfoxide to sulfone (BTO to BTO2, ΔH⧧ = 10.8(5) kcal mol−1 and ΔS⧧ = –21.8(1.6) eu; DBTO to DBTO2, ΔH⧧ = 10.3(9) kcal mol−1 and ΔS⧧ = –25(3) eu) were calculated from variable temperature studies using [Cp*2W2O5]. DFT calculations suggest that the greater reactivity of DBT relative to BT is not caused by ground-state effects but rather by a transition-state effect associated with the greater thermodynamic gain in DBT oxidation.
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hal-03192597 , version 1 (08-04-2021)

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Marco Ciclosi, Chiara Dinoi, Luca Gonsalvi, Maurizio Peruzzini, Eric Manoury, et al.. Oxidation of Thiophene Derivatives with H 2 O 2 in Acetonitrile Catalyzed by [Cp* 2 M 2 O 5 ] (M = Mo, W): A Kinetic Study. Organometallics, 2008, 27 (10), pp.2281-2286. ⟨10.1021/om800035f⟩. ⟨hal-03192597⟩
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