期刊
CHEMISTRY-A EUROPEAN JOURNAL
卷 26, 期 69, 页码 16291-16305出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.202002801
关键词
cyclopentadienides; electron-poor ligands; imidazoliums; ruthenocenes; ylides
资金
- Projekt DEAL
The synthesis of electron-poor mono-, di- and tri(imidazolium)-substituted Cp-ylides is presented and their electronic properties are discussed based on NMR spectroscopy, X-ray structure analyses, electrochemical investigations and DFT calculations as well as by their reactivity toward [Ru(CH3CN)(3)Cp*](PF6). With mono- and di(imidazolium)-substituted cyclopentadienides the respective monocationic and dicationic ruthenocences are formed (X-ray), whereas tri(imidazolium) cyclopentadienides are too electron-poor to form the ruthenocenes. Cyclic voltammetric analysis of the ruthenocenes shows reversible oxidation at a potential that increases with every additional electron-withdrawing imidazolium substituent at the Cp ligand by 0.53-0.55 V in an electrolyte based on a weakly coordinating anion. A reversible oxidation can be observed for the free 1,3-disubstituted ligand as well.
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