bei Google ScholarTitelangaben
Butovskii, Mikhail V. ; Oelkers, Benjamin ; Bauer, Tobias ; Bakker, Jacinta M. ; Bezugly, Viktor ; Wagner, Frank R. ; Kempe, Rhett:
Lanthanoid-transition-metal bonding in bismetallocenes.
In: Chemistry : a European Journal.
Bd. 20
(2014)
Heft 10
.
- S. 2804-2811.
ISSN 1521-3765
DOI: https://doi.org/10.1002/chem.201304125
Abstract
Bismetallocenes Cp2 LuReCp2 and Cp*2 LaReCp2 (Cp=cyclopentadienyl; Cp*=pentamethylcyclopentadienyl) were prepared using different synthetic strategies. Salt metathesis-performed in aromatic hydrocarbons to avoid degradation pathways caused by THF-were identified as an attractive alternative to alkane elimination. Although alkane elimination is more attractive in the sense of its less elaborate workup, the rate of the reaction shows a strong dependence on the ionic radius of Ln(3+) (Ln=lanthanide) within a given ligand set. Steric hindrance can cause a dramatic decrease in the reaction rate of alkane elimination. In this case, salt metathesis should be considered the better alternative. Covalent bonding interactions between the Ln and transition-metal (TM) cations has been quantified on the basis of the delocalization index. Its magnitude lies within the range characteristic for bonds between transition metals. Secondary interactions were identified between carbon atoms of the Cp ligand of the transition metal and the Ln cation. Model calculations clearly indicated that the size of these interactions depends on the capability of the TM atom to act as an electron donor (i.e., a Lewis base). The consequences can even be derived from structural details. The observed clear dependency of the LuRu and interfragment LuC bonding on the THF coordination of the Lu atom points to a tunable Lewis acidity at the Ln site, which provides a method of significantly influencing the structure and the interfragment bonding.
Weitere Angaben
| Publikationsform: | Artikel in einer Zeitschrift |
|---|---|
| Begutachteter Beitrag: | Ja |
| Institutionen der Universität: | 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 > Lehrstuhl Anorganische Chemie II Fakultäten > Fakultät für Biologie, Chemie und Geowissenschaften > Fachgruppe Chemie > Lehrstuhl Anorganische Chemie II > Lehrstuhl Anorganische Chemie II - Univ.-Prof. Dr. Rhett Kempe |
| Titel an der UBT entstanden: | Ja |
| Themengebiete aus DDC: | 500 Naturwissenschaften und Mathematik 500 Naturwissenschaften und Mathematik > 500 Naturwissenschaften 500 Naturwissenschaften und Mathematik > 540 Chemie |
| Eingestellt am: | 10 Mär 2015 07:41 |
| Letzte Änderung: | 10 Mär 2015 08:06 |
| URI: | https://eref.uni-bayreuth.de/id/eprint/7403 |