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Noor, Awal ; Bauer, Tobias ; Todorova, Tanya K. ; Weber, Birgit ; Gagliardi, Laura ; Kempe, Rhett:
The Ligand-Based Quintuple Bond-Shortening Concept and Some of Its Limitations.
In: Chemistry : a European Journal.
Bd. 19
(2013)
Heft 30
.
- S. 9825-9832.
ISSN 1521-3765
DOI: https://doi.org/10.1002/chem.201301240
Abstract
Herein, the ligand-based concept of shortening quintuple bonds and some of its limitations are reported. In dichromium–diguanidinato complexes, the length of the quintuple bond can be influenced by the substituent at the central carbon atom of the used ligand. The guanidinato ligand with a 2,6-dimethylpiperidine backbone was found to be the optimal ligand. The reduction of its chromium(II) chloride–ate complex gave a quintuply bonded bimetallic complex with a Cr[BOND]Cr distance of 1.7056 (12) Å. Its metal–metal distance, the shortest observed in any stable compound yet, is of essentially the same length as that of the longest alkane C[BOND]C bond (1.704 (4) Å). Both molecules, the alkane and the Cr complex, are of remarkable stability. Furthermore, an unsupported CrI dimer with an effective bond order (EBO) of 1.25 between the two metal atoms, indicated by CASSCF/CASPT2 calculations, was isolated as a by-product. The formation of this by-product indicates that with a certain bulk of the guanidinato ligand, other coordination isomers become relevant. Over-reduction takes place, and a chromium–arene sandwich complex structurally related to the classic dibenzene chromium complex was observed, even when bulkier substituents are introduced at the central carbon atom of the used guanidinato ligand.
Weitere Angaben
| Publikationsform: | Artikel in einer Zeitschrift |
|---|---|
| Begutachteter Beitrag: | Ja |
| Institutionen der Universität: | Fakultäten > Fakultät für Biologie, Chemie und Geowissenschaften > Fachgruppe Chemie > Professur Anorganische Chemie IV > Professur Anorganische Chemie IV - Univ.-Prof. Dr. Birgit Weber Fakultäten Fakultäten > Fakultät für Biologie, Chemie und Geowissenschaften Fakultäten > Fakultät für Biologie, Chemie und Geowissenschaften > Fachgruppe Chemie Fakultäten > Fakultät für Biologie, Chemie und Geowissenschaften > Fachgruppe Chemie > Professur Anorganische Chemie IV |
| Titel an der UBT entstanden: | Ja |
| Themengebiete aus DDC: | 500 Naturwissenschaften und Mathematik > 540 Chemie |
| Eingestellt am: | 26 Jul 2017 10:52 |
| Letzte Änderung: | 26 Jul 2017 10:52 |
| URI: | https://eref.uni-bayreuth.de/id/eprint/38817 |