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Experimental and Theoretical Investigation of Simple Terminal Group 6 Arsenide As MF3 Molecules

Wang, Xuefeng; Andrews, Lester; Knitter, Marta; Malmqvist, Per-Åke LU and Roos, Björn LU (2009) In The Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory 113(21). p.6064-6069
Abstract
Laser-ablated group 6 metal atoms react with NF3 and PF3 to form the simple lowest energy N MF3 and P=MX3 products, and this investigation has been extended to AsF3. Mo and W atoms react with AsF3 upon excitation by laser ablation or UV irradiation to form stable trigonal As MF3 terminal arsenides. These molecules are identified by comparison of the closely related infrared spectra of the analogous phosphide species and with frequencies calculated by density functional theory and multiconfigurational second order perturbation theory (CASSCF/CASPT2). Computed CASSCF/CASPT2 triple bond lengths for the As MoF3 and As WF3 molecules are 2.240 angstrom and 2.250 angstrom, respectively. The natural bond orders calculated by CASSCF/CASPT2 decrease... (More)
Laser-ablated group 6 metal atoms react with NF3 and PF3 to form the simple lowest energy N MF3 and P=MX3 products, and this investigation has been extended to AsF3. Mo and W atoms react with AsF3 upon excitation by laser ablation or UV irradiation to form stable trigonal As MF3 terminal arsenides. These molecules are identified by comparison of the closely related infrared spectra of the analogous phosphide species and with frequencies calculated by density functional theory and multiconfigurational second order perturbation theory (CASSCF/CASPT2). Computed CASSCF/CASPT2 triple bond lengths for the As MoF3 and As WF3 molecules are 2.240 angstrom and 2.250 angstrom, respectively. The natural bond orders calculated by CASSCF/CASPT2 decrease from 2.67 to 2.60 for P MoF3 to As MoF3 and from 2.74 to 2.70 for P WF3 to As WF3 as the arsenic valence orbitals are less effective than those of phosphorus in bonding to each metal atom and the larger metal orbital size becomes more compatible with the arsenic valence orbitals. The Cr atom reaction gives the arsinidene AsF=CrF2 product instead of the higher energy As CrF3 molecule as the Cr (VI) state is not supported by the softer pnictides. (Less)
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organization
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Contribution to journal
publication status
published
subject
in
The Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory
volume
113
issue
21
pages
6064 - 6069
publisher
The American Chemical Society
external identifiers
  • wos:000266296500005
  • scopus:66349101928
ISSN
1520-5215
DOI
10.1021/jp901308n
language
English
LU publication?
yes
id
089f3d14-d5a2-4981-b1f1-c9c0036c3236 (old id 1425629)
date added to LUP
2009-07-01 13:54:51
date last changed
2017-01-01 06:16:48
@article{089f3d14-d5a2-4981-b1f1-c9c0036c3236,
  abstract     = {Laser-ablated group 6 metal atoms react with NF3 and PF3 to form the simple lowest energy N MF3 and P=MX3 products, and this investigation has been extended to AsF3. Mo and W atoms react with AsF3 upon excitation by laser ablation or UV irradiation to form stable trigonal As MF3 terminal arsenides. These molecules are identified by comparison of the closely related infrared spectra of the analogous phosphide species and with frequencies calculated by density functional theory and multiconfigurational second order perturbation theory (CASSCF/CASPT2). Computed CASSCF/CASPT2 triple bond lengths for the As MoF3 and As WF3 molecules are 2.240 angstrom and 2.250 angstrom, respectively. The natural bond orders calculated by CASSCF/CASPT2 decrease from 2.67 to 2.60 for P MoF3 to As MoF3 and from 2.74 to 2.70 for P WF3 to As WF3 as the arsenic valence orbitals are less effective than those of phosphorus in bonding to each metal atom and the larger metal orbital size becomes more compatible with the arsenic valence orbitals. The Cr atom reaction gives the arsinidene AsF=CrF2 product instead of the higher energy As CrF3 molecule as the Cr (VI) state is not supported by the softer pnictides.},
  author       = {Wang, Xuefeng and Andrews, Lester and Knitter, Marta and Malmqvist, Per-Åke and Roos, Björn},
  issn         = {1520-5215},
  language     = {eng},
  number       = {21},
  pages        = {6064--6069},
  publisher    = {The American Chemical Society},
  series       = {The Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory},
  title        = {Experimental and Theoretical Investigation of Simple Terminal Group 6 Arsenide As MF3 Molecules},
  url          = {http://dx.doi.org/10.1021/jp901308n},
  volume       = {113},
  year         = {2009},
}