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Bonding Trends in Molecular Compounds of Lanthanides: The Double-Bonded Carbene Cations LnCH(2) (+) (Ln=Sc, Y, La-Lu).

Roos, Björn LU and Pyykkö, Pekka (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.
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author
organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Chemistry: A European Journal
volume
16
issue
1
pages
270 - 275
publisher
John Wiley & Sons
external identifiers
  • wos:000274007900032
  • pmid:19937867
  • scopus:73949100328
ISSN
1521-3765
DOI
10.1002/chem.200902310
language
English
LU publication?
yes
id
8b7b75dc-d184-40c4-8453-0ed7b0aacffb (old id 1511557)
date added to LUP
2009-12-01 10:10:07
date last changed
2018-05-29 11:42:24
@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    = {John Wiley & Sons},
  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},
  volume       = {16},
  year         = {2010},
}