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Chambrier, Isabelle, Rocchigiani, Luca, Hughes, David L, Budzelaar, Peter MH and Bochmann, Manfred 
ORCID: https://orcid.org/0000-0001-7736-5428
(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 (former - to 2024) |
| UEA Research Groups: | Faculty of Science > Research Groups > Chemistry of Light and Energy Faculty of Science > Research Groups > Chemistry of Materials and Catalysis |
| Depositing User: | Pure Connector |
| Date Deposited: | 01 Jun 2018 08:30 |
| Last Modified: | 07 Dec 2024 01:26 |
| URI: | https://ueaeprints.uea.ac.uk/id/eprint/67258 |
| DOI: | 10.1002/chem.201802160 |
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