Bonding Trends in Molecular Compounds of Lanthanides: The Double-Bonded Carbene Cations LnCH(2) (+) (Ln=Sc, Y, La-Lu).
(2010) In Chemistry: A European Journal 16(1). p.270-275- Abstract
- Quasi-relativistic Douglas-Kroll CASPT2 calculations are reported for the title molecules, mainly to provide primary data for a fit of double-bond covalent radii. Indeed, a well-developed sigma(2)pi(2) double bond is identified in all cases. For Eu and Yb, however, it is an excited state. The main valence orbitals of all Ln ions are 6s and 5d. In the sigma bonds, more 5d than 6s character is found at the Ln. The Ln==C bond lengths show a systematic lanthanide contraction of 13 pm from La to Lu. An agostic symmetry breaking is demonstrated for Ce but its effect on the Ln--C length is small.
Please use this url to cite or link to this publication:
https://lup.lub.lu.se/record/1511557
- author
- Roos, Björn LU and Pyykkö, Pekka
- organization
- publishing date
- 2010
- type
- Contribution to journal
- publication status
- published
- subject
- in
- Chemistry: A European Journal
- volume
- 16
- issue
- 1
- pages
- 270 - 275
- publisher
- Wiley-Blackwell
- external identifiers
-
- wos:000274007900032
- pmid:19937867
- scopus:73949100328
- pmid:19937867
- ISSN
- 1521-3765
- DOI
- 10.1002/chem.200902310
- language
- English
- LU publication?
- yes
- additional info
- The information about affiliations in this record was updated in December 2015. The record was previously connected to the following departments: Theoretical Chemistry (S) (011001039)
- id
- 8b7b75dc-d184-40c4-8453-0ed7b0aacffb (old id 1511557)
- date added to LUP
- 2016-04-01 10:19:08
- date last changed
- 2023-01-25 06:48:49
@article{8b7b75dc-d184-40c4-8453-0ed7b0aacffb, abstract = {{Quasi-relativistic Douglas-Kroll CASPT2 calculations are reported for the title molecules, mainly to provide primary data for a fit of double-bond covalent radii. Indeed, a well-developed sigma(2)pi(2) double bond is identified in all cases. For Eu and Yb, however, it is an excited state. The main valence orbitals of all Ln ions are 6s and 5d. In the sigma bonds, more 5d than 6s character is found at the Ln. The Ln==C bond lengths show a systematic lanthanide contraction of 13 pm from La to Lu. An agostic symmetry breaking is demonstrated for Ce but its effect on the Ln--C length is small.}}, author = {{Roos, Björn and Pyykkö, Pekka}}, issn = {{1521-3765}}, language = {{eng}}, number = {{1}}, pages = {{270--275}}, publisher = {{Wiley-Blackwell}}, series = {{Chemistry: A European Journal}}, title = {{Bonding Trends in Molecular Compounds of Lanthanides: The Double-Bonded Carbene Cations LnCH(2) (+) (Ln=Sc, Y, La-Lu).}}, url = {{http://dx.doi.org/10.1002/chem.200902310}}, doi = {{10.1002/chem.200902310}}, volume = {{16}}, year = {{2010}}, }