Aufgrund von Vorbereitungen auf eine neue Version von KOPS, können kommenden Montag und Dienstag keine Publikationen eingereicht werden. (Due to preparations for a new version of KOPS, no publications can be submitted next Monday and Tuesday.)
Type of Publication: | Journal article |
Author: | Pevny, Florian; Winter, Rainer; Eisenstecken, Daniela; Kopacka, Holger; Enk, Barbara; Wurst, Klaus; Müller, Thomas; Bildstein, Benno |
Year of publication: | 2011 |
Published in: | European Journal of Inorganic Chemistry ; 2011 (2011), 19. - pp. 2958-2966. - ISSN 1434-1948 |
DOI (citable link): | https://dx.doi.org/10.1002/ejic.201100226 |
Summary: |
As we have recently shown, the doubly substituted [1,2-O,O]H, [1,2-O,N]H, [1,2-N,N]H, and [1,3-N,N]H pentafulvenes are convenient N/O-functionalized cyclopentadienide (Cp) precursors. Deprotonation of the pentafulvenes by potassium hydride followed by reaction with [Cp*RhCl2]2 or [Cp*IrCl2]2 gave access to the first functionalized rhodocenium and iridocenium salts that contain two acyl and/or imidoyl substituents. These air-stable compounds represent interesting bis(acyl/imidoyl) or mixed acyl/imidoyl metalloligand systems that combine an axially shielding, electrochemically active metallocene moiety with directly attached, conjugating oxygen and/or nitrogen donor sites. The structural properties of these novel metallocene metalloligands in solution and in the solid state were studied by NMR spectroscopy (1H, 13C, 103Rh) and by single-crystal structure analysis. The electrochemical investigations on complexes 5a, 6b, and 7a showed the effect of the appended functional groups on the potential and on the reversibility of the rhodocenium/rhodocene reduction and provided evidence for the dimerization that followed the reduction. Further redox processes that were due to the heteroatom functions included the stepwise reduction of the 1,2-diketo entity of 5a and the oxidation of the 1,2-diimino moiety of 7a.
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Subject (DDC): | 540 Chemistry |
Keywords: | Rhodium, Metallocenes, N ligands, N, O ligands, Electrochemistry |
Bibliography of Konstanz: | Yes |
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PEVNY, Florian, Rainer WINTER, Daniela EISENSTECKEN, Holger KOPACKA, Barbara ENK, Klaus WURST, Thomas MÜLLER, Benno BILDSTEIN, 2011. Redox-Responsive Rhodocenium [O,O], [N,N] and [N,C,N]Metalloligands. In: European Journal of Inorganic Chemistry. 2011(19), pp. 2958-2966. ISSN 1434-1948. Available under: doi: 10.1002/ejic.201100226
@article{Pevny2011Redox-13940, title={Redox-Responsive Rhodocenium [O,O], [N,N] and [N,C,N]Metalloligands}, year={2011}, doi={10.1002/ejic.201100226}, number={19}, volume={2011}, issn={1434-1948}, journal={European Journal of Inorganic Chemistry}, pages={2958--2966}, author={Pevny, Florian and Winter, Rainer and Eisenstecken, Daniela and Kopacka, Holger and Enk, Barbara and Wurst, Klaus and Müller, Thomas and Bildstein, Benno} }
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