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  Lanthanoid–Transition-Metal Bonding in Bismetallocenes

Butovskii, M. V., Oelkers, B., Bauer, T., Bakker, J. M., Bezugly, V., Wagner, F. R., et al. (2014). Lanthanoid–Transition-Metal Bonding in Bismetallocenes. Chemistry - A European Journal, 20, 2804-2811. doi:10.1002/chem.201304125.

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Item Permalink: http://hdl.handle.net/11858/00-001M-0000-0018-0A31-4 Version Permalink: http://hdl.handle.net/11858/00-001M-0000-0018-0A43-B
Genre: Journal Article

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 Creators:
Butovskii, Mikhail V.1, Author
Oelkers, Benjamin1, Author
Bauer, Tobias1, Author
Bakker, Jacinta M.1, Author
Bezugly, Viktor2, Author              
Wagner, Frank R.3, Author              
Kempe, Rhett1, Author
Affiliations:
1external, ou_persistent22              
2Max Planck Institute for Chemical Physics of Solids, Max Planck Society, ou_1863404              
3Frank Wagner, Chemical Metal Science, Max Planck Institute for Chemical Physics of Solids, Max Planck Society, ou_1863409              

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Free keywords: lanthanum, metallocenes, metal–metal interactions, rare earths, transition metals
 Abstract: Bismetallocenes [Cp2LuReCp2] and [Cp*2LaReCp2] (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 Ln3+ (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[BOND]Ru and interfragment Lu[BOND]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.

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Language(s): eng - English
 Dates: 2014-03-01
 Publication Status: Published in print
 Pages: -
 Publishing info: -
 Table of Contents: -
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Title: Chemistry - A European Journal
  Other : Chem. Eur. J.
Source Genre: Journal
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Publ. Info: Weinheim, Germany : VCH Verlagsgesellschaft
Pages: - Volume / Issue: 20 Sequence Number: - Start / End Page: 2804 - 2811 Identifier: ISSN: 0947-6539
CoNE: /journals/resource/954926979058