Non-palindromic (C^C^D) gold(iii) pincer complexes are not accessible by intramolecular oxidative addition of biphenylenes – an experimental and quantum chemical study
Open Access
- 9 June 2021
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in Dalton Transactions
- Vol. 50 (28), 9754-9767
- https://doi.org/10.1039/d1dt00953b
Abstract
We herein report on the synthesis of biphenylenes substituted with a pyridine (N), a phosphine (P) and a carbene (C′) donor as well as a carbene donor with additional pyridine in the lateral position. We describe the synthesis and structures of derived gold(I) complexes, which we tried to use for the synthesis of non-palindromic [(C^C^D)AuIII] pincer complexes by means of an intramolecular oxidative addition of the strained biphenylene ring. However, the anticipated formation of gold(III) complexes failed due to kinetic and thermodynamic reasons, which we extensively investigated by quantum chemical calculations. Furthermore, we shed light on the oxidative addition of biphenylene to two different gold(I) systems reported in the literature. Our comprehensive quantum-chemical analysis is complemented by NMR experiments.Keywords
Funding Information
- Carl-Zeiss-Stiftung
- Studienstiftung des Deutschen Volkes
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