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A combined theoretical and experimental study of simple terminal group 6 nitride and phosphide N MX3 and P MX3 molecules

Wang, Xuefeng; Andrews, Lester; Lindh, Roland LU ; Veryazov, Valera LU and Roos, Björn LU (2008) In The Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory 112(35). p.8030-8037
Abstract
Organometallic complexes containing terminal metal nitrides and phosphides are important synthetic reagents. Laser-ablated group 6 metal atoms react with NF3, PF3, and PCl3 to form the simple lowest energy N MF3, and P MX3 products following insertion and halogen transfer, with the exception of P CrF3, which is a higher energy species and is not observed. The E MX3 pnictide metal trihalide molecules are identified from both argon and neon matrix infrared spectra and frequencies calculated by density functional theory and multiconfigurational second-order perturbation theory (CASSCF/CASPT2). These simple terminal nitrides involve strong triple bonds, which range from 2.80 to 2.77 to 2.59 natural bond order for M = W, Mo, and Cr,... (More)
Organometallic complexes containing terminal metal nitrides and phosphides are important synthetic reagents. Laser-ablated group 6 metal atoms react with NF3, PF3, and PCl3 to form the simple lowest energy N MF3, and P MX3 products following insertion and halogen transfer, with the exception of P CrF3, which is a higher energy species and is not observed. The E MX3 pnictide metal trihalide molecules are identified from both argon and neon matrix infrared spectra and frequencies calculated by density functional theory and multiconfigurational second-order perturbation theory (CASSCF/CASPT2). These simple terminal nitrides involve strong triple bonds, which range from 2.80 to 2.77 to 2.59 natural bond order for M = W, Mo, and Cr, respectively, as computed by CASSCF/CASPT2, and the M N stretching frequencies also follow this order. The terminal phosphides are weaker with bond orders 2.74, 2.67, and 2.18, respectively, as the more diffuse 3p orbitals are less effective for bonding to the more compact metal valence d orbitals. (Less)
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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
112
issue
35
pages
8030 - 8037
publisher
The American Chemical Society
external identifiers
  • wos:000258800400006
  • scopus:52649170959
ISSN
1520-5215
DOI
10.1021/jp804469a
language
English
LU publication?
yes
id
ed737b08-56dd-4a08-a492-a6a833bd3ab4 (old id 1247725)
date added to LUP
2008-11-21 09:52:46
date last changed
2017-01-01 06:18:09
@article{ed737b08-56dd-4a08-a492-a6a833bd3ab4,
  abstract     = {Organometallic complexes containing terminal metal nitrides and phosphides are important synthetic reagents. Laser-ablated group 6 metal atoms react with NF3, PF3, and PCl3 to form the simple lowest energy N MF3, and P MX3 products following insertion and halogen transfer, with the exception of P CrF3, which is a higher energy species and is not observed. The E MX3 pnictide metal trihalide molecules are identified from both argon and neon matrix infrared spectra and frequencies calculated by density functional theory and multiconfigurational second-order perturbation theory (CASSCF/CASPT2). These simple terminal nitrides involve strong triple bonds, which range from 2.80 to 2.77 to 2.59 natural bond order for M = W, Mo, and Cr, respectively, as computed by CASSCF/CASPT2, and the M N stretching frequencies also follow this order. The terminal phosphides are weaker with bond orders 2.74, 2.67, and 2.18, respectively, as the more diffuse 3p orbitals are less effective for bonding to the more compact metal valence d orbitals.},
  author       = {Wang, Xuefeng and Andrews, Lester and Lindh, Roland and Veryazov, Valera and Roos, Björn},
  issn         = {1520-5215},
  language     = {eng},
  number       = {35},
  pages        = {8030--8037},
  publisher    = {The American Chemical Society},
  series       = {The Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory},
  title        = {A combined theoretical and experimental study of simple terminal group 6 nitride and phosphide N MX3 and P MX3 molecules},
  url          = {http://dx.doi.org/10.1021/jp804469a},
  volume       = {112},
  year         = {2008},
}