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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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author
organization
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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
external identifiers
  • wos:000247966600038
  • scopus:34547559088
ISSN
1520-5215
DOI
10.1021/jp071914b
language
English
LU publication?
yes
id
0189a527-68a5-45f3-b0b5-00229a00453b (old id 691616)
date added to LUP
2007-12-18 11:35:03
date last changed
2017-10-01 04:49:48
@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},
  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},
  volume       = {111},
  year         = {2007},
}