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;
1997-01-01

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.
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
File in questo prodotto:
File Dimensione Formato  
J. Mol. Catal. A Chem. 127,1997, 85-94 .pdf

non disponibili

Tipologia: Versione dell'autore revisionata e accettata per la pubblicazione
Dimensione 709.44 kB
Formato Adobe PDF
709.44 kB Adobe PDF   Visualizza/Apri   Richiedi una copia
Pubblicazioni consigliate

Caricamento pubblicazioni consigliate

Licenza Creative Commons
I metadati presenti in IRIS UNIMORE sono rilasciati con licenza Creative Commons CC0 1.0 Universal, mentre i file delle pubblicazioni sono rilasciati con licenza Attribuzione 4.0 Internazionale (CC BY 4.0), salvo diversa indicazione.
In caso di violazione di copyright, contattare Supporto Iris

Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11380/306700
Citazioni
  • ???jsp.display-item.citation.pmc??? ND
  • Scopus 18
  • ???jsp.display-item.citation.isi??? 15
social impact