Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 135, Issue 10, Pages 3887-3896Publisher
AMER CHEMICAL SOC
DOI: 10.1021/ja310866k
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Funding
- MINECO [CTQ2011-28942-CO2-01, CTQ2011-23336, CSD2006-00003, CSD2007-00006]
- Fondos Feder
- Junta de Andalucia [P10-FQM-06292]
- Norwegian Research Council through the CoE Centre for Theoretical and Computational Chemistry (CTCC) [179568/V30]
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The dehydrogenation of n-hexane and cycloalkanes giving n-hexene and cycloalkenes has been observed in the reaction of such hydrocarbons with hydrogen peroxide, in the presence of copper complexes bearing trispyrazolylborate ligands. This catalytic transformation provides the typical oxidation products (alcohol and ketones) with small amounts of the alkenes, a novel feature in this kind of oxidative processes. Experimental data exclude the participation of hydroxyl radicals derived from Fenton-like reaction mechanisms. DFT studies support a copper-oxo active species, which initiates the reaction by H abstraction. Spin crossover from the triplet to the singlet state, which is required to recover the catalyst, yields the major hydroxylation and minor dehydrogenation products. Further calculations suggested that the superoxo and hydroperoxo species are less reactive than the oxo. A complete mechanistic proposal in agreement with all experimental and computational data is proposed.
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