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Lanthanoid-transition-metal bonding in bismetallocenes

Title data

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. Vol. 20 (2014) Issue 10 . - pp. 2804-2811.
ISSN 1521-3765
DOI: https://doi.org/10.1002/chem.201304125

Abstract in another language

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 LuRu and interfragment LuC 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.

Further data

Item Type: Article in a journal
Refereed: Yes
Institutions of the University: Faculties
Faculties > Faculty of Biology, Chemistry and Earth Sciences
Faculties > Faculty of Biology, Chemistry and Earth Sciences > Department of Chemistry
Faculties > Faculty of Biology, Chemistry and Earth Sciences > Department of Chemistry > Chair Anorganic Chemistry II
Faculties > Faculty of Biology, Chemistry and Earth Sciences > Department of Chemistry > Chair Anorganic Chemistry II > Chair Anorganic Chemistry II - Univ.-Prof. Dr. Rhett Kempe
Result of work at the UBT: Yes
DDC Subjects: 500 Science
500 Science > 500 Natural sciences
500 Science > 540 Chemistry
Date Deposited: 10 Mar 2015 07:41
Last Modified: 10 Mar 2015 08:06
URI: https://eref.uni-bayreuth.de/id/eprint/7403