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Tuning the hyperconjugative aromaticity in Au(III)-substituted indoliums
1State Key Laboratory of Physical Chemistry of Solid Surfaces and Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), Fujian Provincial Key Laboratory of Theoretical and Computational Chemistry and Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China. jun.zhu@xmu.edu.cn.
Hyperconjugative aromaticity (HCA) in organometallics is sensitive to the transition metal
Area of Science:
- Organometallic Chemistry
- Computational Chemistry
- Aromaticity Studies
Background:
- Aromaticity, a core chemical concept, has expanded to include organometallic compounds.
- Hyperconjugative aromaticity (HCA) has been observed in transition metal systems via substituent hyperconjugation.
- The influence of transition metal oxidation states on HCA remains largely unexplored.
Purpose of the Study:
- To investigate the effect of transition metal oxidation state on hyperconjugative aromaticity (HCA).
- To explore the tunability of HCA in organometallic systems with varying gold oxidation states.
Main Methods:
- Density functional theory (DFT) calculations were employed.
- The study focused on indolium systems with gold substituents.
Main Results:
- HCA was found to be absent in indoliums with Au(III) substituents, contrasting with Au(I) systems.
- Ligand modification and cis-trans isomerization allowed for the restoration or enhancement of HCA in Au(III) indoliums.
Conclusions:
- The oxidation state of transition metal substituents significantly impacts HCA.
- HCA in gold-substituted indoliums can be modulated through structural and electronic tuning.
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