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Organometallic Nucleophiles and Pd: What Makes ZnMe2 Different? Is Au Like Zn?
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    Organometallic Nucleophiles and Pd: What Makes ZnMe2 Different? Is Au Like Zn?
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    IU CINQUIMA/Química Inorgánica, Facultad de Ciencias, Universidad de Valladolid, 47011Valladolid, Spain
    Departamento de Química Orgánica, Facultad de Química, Universidad de Vigo, Campus As Lagoas-Marcosende, 36310 Vigo, Spain
    *(J.A.C.) E-mail: [email protected]
    *(R.A.) E-mail: [email protected]
    *(P.E.) E-mail: [email protected]
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    Organometallics

    Cite this: Organometallics 2015, 34, 13, 3120–3128
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    https://doi.org/10.1021/acs.organomet.5b00329
    Published June 18, 2015
    Copyright © 2015 American Chemical Society

    Abstract

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    The cis/trans isomerization of [PdMeAr(PR3)2] complexes (Ar = C6F5, C6F3Cl2) can take place spontaneously (via dissociation and topomerization, studied experimentally) or be catalyzed by ZnMe2. The latter mechanism, studied by DFT methods, involves methyl exchange between Pd and Zn. The study of this catalyzed isomerization shows that, in contrast with the typical acidic behavior of Zn in ZnMeCl, Zn in ZnMe2 (or, more exactly, the ZnMe bond) behaves as a strong basic center, able to attack the relatively high in energy acceptor orbital at Pd in fairly electron rich Pd complexes such as [PdArMeL2] or [PdMe2L2]. This makes the two reagents very different in Negishi couplings. The catalyzed isomerization occurs via transmetalation; thus, both processes are connected. A comparison of the Pd/Zn intermediates and transition states with those found previously for Pd/Au transmetalations reveals very similar structures with intermetallic distances in the order of or noticeably shorter than the sum of the vdW radii, regardless of the nature of the metal (metallophilic Au or nonmetallophillic Zn). These short distances are associated with the involvement of the metals in 3c2e electron deficient bonds during R group transmetalation. In this respect, there is a remarkable similarity to the structurally known behavior of main-group electron-deficient compounds, which supports a unified view of the transmetalation processes.

    Copyright © 2015 American Chemical Society

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    Text, figures, tables, containing experimental and kinetic details, computational information, and calculated structures. The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.organomet.5b00329.

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    Cited By

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    This article is cited by 24 publications.

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    Organometallics

    Cite this: Organometallics 2015, 34, 13, 3120–3128
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.organomet.5b00329
    Published June 18, 2015
    Copyright © 2015 American Chemical Society

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