| Publication Type |
Journal Article |
| Title |
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 |
| Authors |
Maxim L. Kuznetsov Yuriy N. Kozlov Dalmo Mandelli Armando J.L. Pombeiro Georgiy B. Shul'pin |
| Groups |
CCC |
| Journal |
INORGANIC CHEMISTRY |
| Year |
2011 |
| Month |
May |
| Volume |
50 |
| Number |
9 |
| Pages |
3996-4005 |
| Abstract |
A radical mechanism of hydrocarbon oxidations with the environmentally friendly and cheap homogeneous nontransition metal system [Al(H2O)(6)](3+)/H2O2/MeCN-H2O was proposed for the first time on the basis of DFT calculations. A dramatic activation of H2O2 toward homolysis in the key intermediate [Al(H2O)(4)(OOH)(H2O2)(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. |
| DOI |
http://dx.doi.org/10.1021/ic102476x |
| ISBN |
|
| Publisher |
|
| Book Title |
|
| ISSN |
0020-1669 |
| EISSN |
|
| Conference Name |
|
| Bibtex ID |
ISI:000289710700018 |
| Observations |
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