Mechanism of Al3+-Catalyzed Oxidations of Hydrocarbons: Dramatic Activation of H2O2 toward O-O Homolysis in Complex [Al(H2O)(4)(OOH)(H2O2)](2+) Explains the Formation of HO center dot Radicals

Author(s)

Kuznetsov, Maxim L. ^[1] ; Kozlov, Yuriy N. ^[2] ; Mandelli, Dalmo ^[3] ; Pombeiro, Armando J. L. ^[1] ; Shul'pin, Georgiy B. ^[2]

Affiliation

^[1] Univ Tecn Lisboa, Inst Super Tecn, Ctr Quim Estrutural, P-1049001 Lisbon - Portugal

^[2] Russian Acad Sci, Semenov Inst Chem Phys, Moscow 119991 - Russia

^[3] Univ Fed ABC, Ctr Ciencias Nat & Humanas, BR-09210170 Santo Andre, SP - Brazil

• Document type: Journal article
• Source: Inorganic Chemistry; v. 50, n. 9, p. 3996-4005, MAY 2 2011.
• Web of Science Citations: 40

Abstract

A radical mechanism of hydrocarbon oxidations with the environmentally friendly and cheap homogeneous nontransition metal system {[}Al(H(2)O)(6)](3+)/H(2)O(2)/MeCN-H(2)O was proposed for the first time on the basis of DFT calculations. A dramatic activation of H(2)O(2) toward homolysis in the key intermediate {[}Al(H(2)O)(4)(OOH)(H(2)O(2))(2+) due to the presence of the easily oxidizable OOH coligand provides, without a change of metal oxidation state, the generation of HO(center dot) radicals, which then oxidize hydrocarbons. Nonradical mechanisms of the olefin epoxidation with the same catalytic system were also investigated. (AU)

• FAPESP's process: 06/03996-6 - Oxidation of organic compounds including natural products catalysed by transitions metals: Mn, Os and Cu
• Grantee: Dalmo Mandelli
• Support Opportunities: Regular Research Grants