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.
Data di pubblicazione: | 1997 |
Titolo: | Reactivity of transition-metal-modified, Keggin-type heteropolycomplexes in the homogeneous oxidation of cyclohexane and adamantane |
Autore/i: | Cramarossa, Maria Rita; Forti, Luca; M. A., Fedotov; L. G., Detusheva; V. A., Likholobov; L. I., Kuznetsova; G. L., Semin; F., Cavani; F., Trifirò |
Autore/i UNIMORE: | |
Digital Object Identifier (DOI): | http://dx.doi.org/10.1016/S1381-1169(97)00111-8 |
Rivista: | |
Volume: | 127 |
Pagina iniziale: | 85 |
Pagina finale: | 94 |
Codice identificativo ISI: | WOS:000071044900008 |
Codice identificativo Scopus: | 2-s2.0-0031450473 |
Citazione: | 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. |
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