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Rhodocenium Monocarboxylic Acid Hexafluoridophosphate and Its Derivatives : Synthesis, Spectroscopy, Structure, and Electrochemistry

Rhodocenium Monocarboxylic Acid Hexafluoridophosphate and Its Derivatives : Synthesis, Spectroscopy, Structure, and Electrochemistry

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JOCHRIEM, Markus, Larissa A. CASPER, Stefan VANICEK, Dirk PETERSEN, Holger KOPACKA, Klaus WURST, Thomas MÜLLER, Rainer F. WINTER, Benno BILDSTEIN, 2020. Rhodocenium Monocarboxylic Acid Hexafluoridophosphate and Its Derivatives : Synthesis, Spectroscopy, Structure, and Electrochemistry. In: European Journal of Inorganic Chemistry (EurJIC). Wiley. 2020(14), pp. 1300-1310. ISSN 1434-2421. eISSN 1434-1948. Available under: doi: 10.1002/ejic.202000071

@article{Jochriem2020-04-16Rhodo-49844, title={Rhodocenium Monocarboxylic Acid Hexafluoridophosphate and Its Derivatives : Synthesis, Spectroscopy, Structure, and Electrochemistry}, year={2020}, doi={10.1002/ejic.202000071}, number={14}, volume={2020}, issn={1434-2421}, journal={European Journal of Inorganic Chemistry (EurJIC)}, pages={1300--1310}, author={Jochriem, Markus and Casper, Larissa A. and Vanicek, Stefan and Petersen, Dirk and Kopacka, Holger and Wurst, Klaus and Müller, Thomas and Winter, Rainer F. and Bildstein, Benno} }

Vanicek, Stefan Bildstein, Benno 2020-06-16T07:49:59Z Rhodocenium Monocarboxylic Acid Hexafluoridophosphate and Its Derivatives : Synthesis, Spectroscopy, Structure, and Electrochemistry Petersen, Dirk Müller, Thomas terms-of-use As an extension of our continuing work in metallocenium chemistry, we report here on new functionalized rhodocenium salts. In contrast to isoelectronic cobaltocenium compounds, rhodium as a 4d metal allows synthetic routes via prefunctionalized cyclopentadienyl half‐sandwich precursors, thereby facilitating access to monofunctionalized rhodocenium salts containing substituents comprising methyl, trimethylsilyl, carboxylate and carboxylate ester as well as amide derivatives. Synthetic aspects, scope and limitations, as well as spectroscopic (<sup>1</sup>H/<sup>13</sup>C‐NMR, IR, HR‐MS), and structural (XRD) properties are reported. Like the parent rhodocenium ion, all new derivatives undergo two chemically consecutive reductions at potentials that depend on the respective ring substituent. The second reduction competes with a rapid reaction of the corresponding rhodocenes to their 18 VE dimers. Rate constants for this process range from 2 × 10<sup>3</sup> s<sup>–1</sup> to 2.5 × 10<sup>5</sup> s<sup>–1</sup> as estimated from digital simulations of experimental voltammograms. Rhodocenium carboxylic acid (8 ) constitutes a special case in that proton instead of metal reduction is observed at Pt or Au electrodes. Kopacka, Holger Casper, Larissa A. Müller, Thomas eng Petersen, Dirk 2020-06-16T07:49:59Z Jochriem, Markus Kopacka, Holger Jochriem, Markus Wurst, Klaus Vanicek, Stefan Winter, Rainer F. Casper, Larissa A. Bildstein, Benno 2020-04-16 Wurst, Klaus Winter, Rainer F.

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