Oxidation of Thiophene Derivatives with H2O2 in Acetonitrile Catalyzed by [Cp*2M2O5] (M = Mo, W): A Kinetic Study
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- 作者：Marco Ciclosi ; Chiara Dinoi ; Luca Gonsalvi ; Maurizio Peruzzini ; Eric Manoury ; Rinaldo Poli
- 刊名：Organometallics
- 出版年：2008
- 出版时间：May 26, 2008
- 年：2008
- 卷：27
- 期：10
- 页码：2281 - 2286
- 全文大小：334K
- 年卷期：v.27,no.10(May 26, 2008)
- ISSN：1520-6041
文摘
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.
= 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.