The oxidation of cyclohexane and adamantane catalyzed by Keggin-type transition-metal-containing heteropolycomplexes (TMC-HPCs) is reported. The reactions were carried out at 20 degrees C in CCl4 or in CH2Cl2 as reaction solvent in the presence of t-butylhydroperoxide (t-BuOOH) as oxidizing agent. A radical chain mechanism of oxidation by t-BuOOH in the presence of molecular oxygen is proposed for all complexes tested, involving a R-H hydrogen atom abstraction by an intermediate active form of the TMC-HPC. Under the examined conditions molecular oxygen was necessary to initiate the reaction, The preparation of Co(II), Fe(III) and Cr(III)-HPC samples and their composition under reaction conditions are also discussed, based on P-31-NMR and W-VIS absorption spectra.

Reactivity of transition-metal-modified, Keggin-type heteropolycomplexes in the homogeneous oxidation of cyclohexane and adamantane / Cramarossa, Maria Rita; Forti, Luca; M. A., Fedotov; L. G., Detusheva; V. A., Likholobov; L. I., Kuznetsova; G. L., Semin; F., Cavani; F., Trifirò. - In: JOURNAL OF MOLECULAR CATALYSIS. A: CHEMICAL. - ISSN 1381-1169. - STAMPA. - 127:(1997), pp. 85-94. [10.1016/S1381-1169(97)00111-8]

Reactivity of transition-metal-modified, Keggin-type heteropolycomplexes in the homogeneous oxidation of cyclohexane and adamantane

CRAMAROSSA, Maria Rita;FORTI, Luca;
1997

Abstract

The oxidation of cyclohexane and adamantane catalyzed by Keggin-type transition-metal-containing heteropolycomplexes (TMC-HPCs) is reported. The reactions were carried out at 20 degrees C in CCl4 or in CH2Cl2 as reaction solvent in the presence of t-butylhydroperoxide (t-BuOOH) as oxidizing agent. A radical chain mechanism of oxidation by t-BuOOH in the presence of molecular oxygen is proposed for all complexes tested, involving a R-H hydrogen atom abstraction by an intermediate active form of the TMC-HPC. Under the examined conditions molecular oxygen was necessary to initiate the reaction, The preparation of Co(II), Fe(III) and Cr(III)-HPC samples and their composition under reaction conditions are also discussed, based on P-31-NMR and W-VIS absorption spectra.
1997
127
85
94
Reactivity of transition-metal-modified, Keggin-type heteropolycomplexes in the homogeneous oxidation of cyclohexane and adamantane / Cramarossa, Maria Rita; Forti, Luca; M. A., Fedotov; L. G., Detusheva; V. A., Likholobov; L. I., Kuznetsova; G. L., Semin; F., Cavani; F., Trifirò. - In: JOURNAL OF MOLECULAR CATALYSIS. A: CHEMICAL. - ISSN 1381-1169. - STAMPA. - 127:(1997), pp. 85-94. [10.1016/S1381-1169(97)00111-8]
Cramarossa, Maria Rita; Forti, Luca; M. A., Fedotov; L. G., Detusheva; V. A., Likholobov; L. I., Kuznetsova; G. L., Semin; F., Cavani; F., Trifirò...espandi
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11380/306700
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