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dc.contributor.authorNeuenschwander, Ulrich
dc.contributor.authorNegron, Arnaldo
dc.contributor.authorJensen, Klavs F.
dc.date.accessioned2015-01-09T19:08:28Z
dc.date.available2015-01-09T19:08:28Z
dc.date.issued2013-05
dc.date.submitted2013-04
dc.identifier.issn1089-5639
dc.identifier.issn1520-5215
dc.identifier.urihttp://hdl.handle.net/1721.1/92773
dc.description.abstractClock reactions are rare kinetic phenomena, so far limited mostly to systems with ionic oxoacids and oxoanions in water. We report a new clock reaction in cyclohexanol that forms molybdenum blue from a noncharged, yellow molybdenum complex as precursor, in the presence of hydrogen peroxide. Interestingly, the concomitant color change is reversible, enabling multiple clock cycles to be executed consecutively. The kinetics of the clock reaction were experimentally characterized, and by adding insights from quantum chemical calculations, a plausible reaction mechanism was postulated. Key elementary reaction steps comprise sigmatropic rearrangements with five-membered or bicyclo[3.1.0] transition states. Importantly, numerical kinetic modeling demonstrated the mechanism’s ability to reproduce the experimental findings. It also revealed that clock behavior is intimately connected to the sudden exhaustion of hydrogen peroxide. Due to the stoichiometric coproduction of ketone, the reaction bears potential for application in alcohol oxidation catalysis.en_US
dc.description.sponsorshipSwiss National Science Foundationen_US
dc.language.isoen_US
dc.publisherAmerican Chemical Society (ACS)en_US
dc.relation.isversionofhttp://dx.doi.org/10.1021/jp400879den_US
dc.rightsArticle is made available in accordance with the publisher's policy and may be subject to US copyright law. Please refer to the publisher's site for terms of use.en_US
dc.sourceProf. Jensen via Erja Kajosaloen_US
dc.titleA Clock Reaction Based on Molybdenum Blueen_US
dc.typeArticleen_US
dc.identifier.citationNeuenschwander, Ulrich, Arnaldo Negron, and Klavs F. Jensen. “A Clock Reaction Based on Molybdenum Blue.” The Journal of Physical Chemistry A 117, no. 21 (May 30, 2013): 4343–4351.en_US
dc.contributor.departmentMassachusetts Institute of Technology. Department of Chemical Engineeringen_US
dc.contributor.approverJensen, Klavs F.en_US
dc.contributor.mitauthorNeuenschwander, Ulrichen_US
dc.contributor.mitauthorNegron, Arnaldoen_US
dc.contributor.mitauthorJensen, Klavs F.en_US
dc.relation.journalThe Journal of Physical Chemistry Aen_US
dc.eprint.versionAuthor's final manuscripten_US
dc.type.urihttp://purl.org/eprint/type/JournalArticleen_US
eprint.statushttp://purl.org/eprint/status/PeerRevieweden_US
dspace.orderedauthorsNeuenschwander, Ulrich; Negron, Arnaldo; Jensen, Klavs F.en_US
dc.identifier.orcidhttps://orcid.org/0000-0001-7192-580X
mit.licensePUBLISHER_POLICYen_US


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