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Structure and Bonding of [E−Cp−E′]+ Complexes (E and E′ = B−Tl; Cp = Cyclopentadienyl)

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    Structure and Bonding of [E−Cp−E′]+ Complexes (E and E′ = B−Tl; Cp = Cyclopentadienyl)
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    Fachbereich Chemie, Philipps-Universität Marburg, Hans-Meerwein-Strasse, D-35042 Marburg, Germany, and Facultad de Química, Universidad de Guanajuato, Noria Alta s/n CP 36050, Guanajuato, Gto. México
    * Corresponding author. E-mail: [email protected]; [email protected]
    †Philipps-Universität Marburg.
    ‡Universidad de Guanajuato.
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    Organometallics

    Cite this: Organometallics 2008, 27, 6, 1106–1111
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    https://doi.org/10.1021/om700994y
    Published February 22, 2008
    Copyright © 2008 American Chemical Society
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    Abstract

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    The geometries and metal–ligand bond dissociation energies of [E−Cp−E′]+ complexes (E, E′ = group 13 element; Cp = cyclopentadienyl) have been calculated within the density functional theory framework. The geometries of the title complexes were optimized at the BP86 level with the TZ2P valence basis set. The nature of the metal–ligand bonding has been studied using the energy decomposition analysis (EDA). The calculated bond strengths for the homoleptic complexes [E−Cp−E]+ with respect to loss of a neutral or charged group 13 atom are Ga > Al > In > Tl ≫ B. While the energetically most favorable pathway for the boron complex [B−Cp−B]+ is the loss of a neutral boron atom, heavier homologues [E−Cp−E]+ (E = Al−Tl) dissociate via loss of the charged atom E+. The heteroleptic species [E−Cp−E′]+ are less stable than the homoleptic complexes [E−Cp−E]+. The lowest energy pathway for dissociation is the loss of the positively charged heavier atom E′+. The B−Cp interactions in the boron complexes have a larger (covalent) orbital character than the E−Cp bonding in the heavier homologues. The energy decomposition analysis of [E−Cp−E′]+, using Cp− and (E···E′)2+ as ligands, suggests that the a1(σ) bonding has nearly the same strength as the e1(π) bonding.

    Copyright © 2008 American Chemical Society

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    Cartesian coordinates (in Å) and total energies (in au) of all the stationary points discussed in the text are available free of charge via the Internet at http://pubs.acs.org.

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    Organometallics

    Cite this: Organometallics 2008, 27, 6, 1106–1111
    Click to copy citationCitation copied!
    https://doi.org/10.1021/om700994y
    Published February 22, 2008
    Copyright © 2008 American Chemical Society
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