Thermally stable gold(III) alkene and alkyne complexes: Synthesis, structures, and assessment of the trans‐influence on gold‐ligand bond enthalpies

Chambrier, Isabelle, Rocchigiani, Luca, Hughes, David L, Budzelaar, Peter MH and Bochmann, Manfred (2018) Thermally stable gold(III) alkene and alkyne complexes: Synthesis, structures, and assessment of the trans‐influence on gold‐ligand bond enthalpies. Chemistry - A European Journal, 24 (44). pp. 11467-11474. ISSN 0947-6539

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    Abstract

    The reaction of [C^C)Au(OEt2)2]+ with 1,5‐cyclooctadiene or norbornadiene affords the corresponding olefin complexes [(C^C)Au(COD)]SbF6 and [(C^C)Au(NBD)]SbF6, which are thermally stable in solution and the solid state (C^C = 4,4′‐di‐t‐butylbiphenyl‐2,2′‐diyl). The crystal structures of these complexes have been determined. By contrast, dienones such as dibenzylideneacetone are O‐ rather than C=C‐bonded. The reactions of (C^C)Au(OAcF)(L) (L = PMe3 or CNxyl) with B(C6F5)3 in the presence of bis(1‐adamantyl)acetylene give the mixed‐ligand alkyne complexes [(C^C)Au(AdC≡CAd)(L)]+, the first complexes of their type in gold chemistry. In the presence of an excess of acetylene these compounds are thermally stable in solution and as solids. The bonding of n‐ and π‐donor ligands to Au(III) fragments and the effect of the trans influence exerted by N‐ and C‐donors was explored with the aid of DFT calculations. Results show that the Au‐L bond enthalpies trans to anionic C are 35 ‐ 60% of the enthalpies trans to N, with strong π‐acceptors being particularly affected. In comparison with [Me2Au]+, the [(C^C)Au]+ fragment is more polar and in bond enthalpy terms resembles Me2Pt.

    Item Type: Article
    Uncontrolled Keywords: gold,alkene,alkyne,bond energy,dft calculation
    Faculty \ School: Faculty of Science > School of Chemistry
    Depositing User: Pure Connector
    Date Deposited: 01 Jun 2018 09:30
    Last Modified: 19 Jun 2019 07:30
    URI: https://ueaeprints.uea.ac.uk/id/eprint/67258
    DOI: 10.1002/chem.201802160

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