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Theoretical Structure–Reactivity Study of Ethylene Insertion into Nickel–Alkyl Bonds. A Kinetically Significant and Unanticipated Role of trans Influence in Determining Agostic Bond Strengths
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    Theoretical Structure–Reactivity Study of Ethylene Insertion into Nickel–Alkyl Bonds. A Kinetically Significant and Unanticipated Role of trans Influence in Determining Agostic Bond Strengths
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    Department of Chemistry, The American University of Beirut, Beirut, Lebanon
    Department of Chemistry and Chemical Biology, Rutgers, The State University of New Jersey, New Brunswick, New Jersey 08903, United States
    § Laboratoire de Chimie de Coordination, Institut de Chimie (UMR 7177 CNRS), Université de Strasbourg, F-67081 Strasbourg Cédex, France
    *E-mail: [email protected] (F.H.); [email protected] (K.K.-J.); [email protected] (A.S.G.).
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    Organometallics

    Cite this: Organometallics 2012, 31, 13, 4680–4692
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    https://doi.org/10.1021/om300001n
    Published June 25, 2012
    Copyright © 2012 American Chemical Society

    Abstract

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    Theoretical methods (B3LYP, M06, and CCSD(T)) have been used to study the kinetics and thermodynamics of ethyl migratory insertion in a series of square-planar [(XY)Ni(ethyl)(ethylene)] complexes (XY = anionic bidentate ligand). The results are discussed qualitatively using general trans-influence arguments. When X ≠ Y, the reactions of the two possible isomers have been compared. The results reveal that when one of the coordinating groups exerts a strong trans influence (STI) and the other a weak trans influence (WTI), as in a STIWTI chelating ligand such as a phosphino-enolate (PO), one of the two isomers has an activation energy for ethylene insertion (i.e., ethyl migration) that is much less than that calculated for symmetrical bidentate ligands of either the WTIWTI or STISTI types. Specifically, a low activation energy is found when an ethyl group, coordinated trans to the STI group, migrates to the ethylene coordinated trans to the WTI group. The converse pathway in the STIWTI system, wherein ethyl migrates from a position trans to a WTI group, encounters a very high barrier. However, the kinetic barrier to isomerization (prior to migration) is sufficiently low to allow repeated insertions to proceed via the low-barrier pathway, in which an alkyl group in effect migrates from the position trans to the STI group to the position trans to the WTI group. The overall barrier (isomerization plus insertion) for an [(STIWTI)Ni(ethyl)(ethylene)] complex is less than that calculated for insertion in a WTIWTI analogue. Ethylene dissociation from [(XY)Ni(ethyl)(ethylene)] leads to an intermediate exhibiting a Ni–ethyl β-agostic bond. Unexpectedly, the data reveal that increased trans influence exerted by the ligand trans to the ethyl α-carbon results in a strengthening of the β-agostic interactions. The [(STISTI)Ni(ethyl)] species, therefore, have a surprisingly low energy agostic resting state. As a result, ethylene binding to [(STISTI)Ni(ethyl)] is predicted to be endoergic; this contributes to an overall barrier to catalytic ethylene insertion which is greater than that calculated for (STIWTI)Ni-based species. These results may explain, at least in part, the favorable role of STIWTI chelating ligands in nickel-catalyzed olefin oligomerization. They likely also have bearing on factors influencing the activity of late-transition-metal catalysts for olefin oligomerization and polymerization more generally.

    Copyright © 2012 American Chemical Society

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    Supporting Information

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    Tables giving relative B3LYP/6-311G(2d,2p) and M06/6-311++G(2d,2p) electronic energies, enthalpies, entropies, and free energies, in the gas and solvent dielectric continuum, and Cartesian coordinates and absolute energies for the B3LYP/6-311G(2d,2p) minima and transition states used in the figures and text giving the complete ref 33. This material is available free of charge via the Internet at http://pubs.acs.org.

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    Organometallics

    Cite this: Organometallics 2012, 31, 13, 4680–4692
    Click to copy citationCitation copied!
    https://doi.org/10.1021/om300001n
    Published June 25, 2012
    Copyright © 2012 American Chemical Society

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