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Inverse H/D Isotope Effects in Benzene Activation by Cationic and Anionic Cobalt Clusters
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    Inverse H/D Isotope Effects in Benzene Activation by Cationic and Anionic Cobalt Clusters
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    Fachbereich Chemie and Forschungszentrum OPTIMAS, Technische Universität Kaiserslautern, 67663 Kaiserslautern, Germany
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    The Journal of Physical Chemistry A

    Cite this: J. Phys. Chem. A 2013, 117, 6, 1197–1203
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    https://doi.org/10.1021/jp305281m
    Published December 18, 2012
    Copyright © 2012 American Chemical Society

    Abstract

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    Reactions under single collision conditions with benzene C6H6 and with benzene-d6 C6D6 of size selected cationic cobalt clusters Con+ and of anionic cobalt clusters Con in the cluster size range n = 3–28 revealed that dehydrogenation by cationic clusters is sparse, whereas it is ubiquitous in reactions by anionic clusters. Kinetic isotope effects (KIE) in total reaction rates are inverse and, in part, large. Dehydrogenation isotope effects (DIE) are normal. A multistep model of adsorption and stepwise dehydrogenation from the precursor adsorbate unravels a possible origin of the inverse KIE: Single step C–H bond activation is swift (no KIE in forward direction) and largely reversible (normal KIE backward) whereas H/D tunneling is likely to contribute (backward). DFT calculations of the structures and energetics along the reaction path in [Co13C6H6]+ lend support to the proposed multistep model. The observed effects on rates and KIEs of cluster charges and of cluster sizes are noted to elucidate further.

    Copyright © 2012 American Chemical Society

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    Supporting Information

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    Figures showing relative partial rate constants for the reaction of Con+ and of Con with perdeuterobenzene. A scheme for energetics of the benzene cobalt interaction as a function of cobalt sample size. A qualitative scheme of the energetics along the reaction coordinate of C–H bond activations in Con± + C6H6 as compared to Nbn± + C6H6 and Rhn± + C6H6. Figures of calculated structure of Co13(C6H6)+, Co13(H)(C6H5)+, and Co13(H)(H)(C6H4)+. The full reference to the Gaussian program package. This material is available free of charge via the Internet at http://pubs.acs.org.

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    This article is cited by 11 publications.

    1. Wen Gan, Lijun Geng, Baoqi Yin, Hanyu Zhang, Zhixun Luo, Klavs Hansen. Cyclotrimerization of Acetylene on Clusters Con+/Fen+/Nin+(n = 1–16). The Journal of Physical Chemistry A 2021, 125 (48) , 10392-10400. https://doi.org/10.1021/acs.jpca.1c09015
    2. Manisha Ray, Richard N. Schaugaard, Josey E. Topolski, Jared O. Kafader, Krishnan Raghavachari, and Caroline Chick Jarrold . Molybdenum Oxide Cluster Anion Reactions with C2H4 and H2O: Cooperativity and Chemifragmentation. The Journal of Physical Chemistry A 2018, 122 (1) , 41-52. https://doi.org/10.1021/acs.jpca.7b10798
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    4. Konrad Koszinowski. Mass Spectrometry of Organocobalt Derivatives. 2022, 1-20. https://doi.org/10.1002/9780470682531.pat0998
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    9. K. Zhou, C. B. Zhao, W. D. Huang. Theoretical study of structure, bonding, and electronic behavior of novel sandwich complexes Os3(C6H6) n (n = 1, 2). Russian Journal of Physical Chemistry A 2017, 91 (11) , 2170-2175. https://doi.org/10.1134/S0036024417110383
    10. Jared O. Kafader, Manisha Ray, Krishnan Raghavachari, Caroline Chick Jarrold. Role of weakly bound complexes in temperature-dependence and relative rates of Mx O y − + H2O ( M = Mo, W) reactions. The Journal of Chemical Physics 2016, 144 (7) https://doi.org/10.1063/1.4941829
    11. Gereon Niedner-Schatteburg. Cooperative Effects in Clusters and Oligonuclear Complexes of Transition Metals in Isolation. 2016, 1-40. https://doi.org/10.1007/430_2016_11

    The Journal of Physical Chemistry A

    Cite this: J. Phys. Chem. A 2013, 117, 6, 1197–1203
    Click to copy citationCitation copied!
    https://doi.org/10.1021/jp305281m
    Published December 18, 2012
    Copyright © 2012 American Chemical Society

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