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Agostic interaction in the methylidene metal dihydride complexes H2MCH2 (M = Y, Zr, Nb, Mo, Ru, Th, or U)

Roos, Björn LU ; Lindh, Roland LU ; Cho, Han-Gook and Andrews, Lester (2007) In The Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory 111(28). p.6420-6424
Abstract
Multiconfigurational quantum chemical methods (complete active space self-consistent field (CASSCF)/second-order perturbation theory (CASPT2)) have been used to study the agostic interaction between the metal atom and H(C) in the methylidene metal dihydride complexes H2MCH2, where M is a second row transition metal or the actinide atoms Th or U. The geometry of some of these complexes is highly irregular due to the formation of a three center bond CH center dot center dot center dot M, where the electrons in the CH bond are delocalized onto empty or half empty orbitals of d- or f-type on the metal. No agostic interaction is expected when M = Y, where only a single bond with methylene can be formed, or when M = Ru, because of the lack of... (More)
Multiconfigurational quantum chemical methods (complete active space self-consistent field (CASSCF)/second-order perturbation theory (CASPT2)) have been used to study the agostic interaction between the metal atom and H(C) in the methylidene metal dihydride complexes H2MCH2, where M is a second row transition metal or the actinide atoms Th or U. The geometry of some of these complexes is highly irregular due to the formation of a three center bond CH center dot center dot center dot M, where the electrons in the CH bond are delocalized onto empty or half empty orbitals of d- or f-type on the metal. No agostic interaction is expected when M = Y, where only a single bond with methylene can be formed, or when M = Ru, because of the lack of empty electron accepting metal valence orbitals. The largest agostic interaction is found in the Zr and U complexes. (Less)
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publishing date
type
Contribution to journal
publication status
published
subject
in
The Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory
volume
111
issue
28
pages
6420 - 6424
publisher
The American Chemical Society (ACS)
external identifiers
  • wos:000247966600038
  • scopus:34547559088
  • pmid:17580834
ISSN
1520-5215
DOI
10.1021/jp071914b
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
0189a527-68a5-45f3-b0b5-00229a00453b (old id 691616)
date added to LUP
2016-04-01 16:50:40
date last changed
2023-04-08 12:52:06
@article{0189a527-68a5-45f3-b0b5-00229a00453b,
  abstract     = {{Multiconfigurational quantum chemical methods (complete active space self-consistent field (CASSCF)/second-order perturbation theory (CASPT2)) have been used to study the agostic interaction between the metal atom and H(C) in the methylidene metal dihydride complexes H2MCH2, where M is a second row transition metal or the actinide atoms Th or U. The geometry of some of these complexes is highly irregular due to the formation of a three center bond CH center dot center dot center dot M, where the electrons in the CH bond are delocalized onto empty or half empty orbitals of d- or f-type on the metal. No agostic interaction is expected when M = Y, where only a single bond with methylene can be formed, or when M = Ru, because of the lack of empty electron accepting metal valence orbitals. The largest agostic interaction is found in the Zr and U complexes.}},
  author       = {{Roos, Björn and Lindh, Roland and Cho, Han-Gook and Andrews, Lester}},
  issn         = {{1520-5215}},
  language     = {{eng}},
  number       = {{28}},
  pages        = {{6420--6424}},
  publisher    = {{The American Chemical Society (ACS)}},
  series       = {{The Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory}},
  title        = {{Agostic interaction in the methylidene metal dihydride complexes H2MCH2 (M = Y, Zr, Nb, Mo, Ru, Th, or U)}},
  url          = {{http://dx.doi.org/10.1021/jp071914b}},
  doi          = {{10.1021/jp071914b}},
  volume       = {{111}},
  year         = {{2007}},
}