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Title: Theoretical study of cyanophosphapropyne (NCCP), isocyanophosphapropyne (CNCP) and their isomers: stability and properties
Authors: Pham-Tran, N N ×
Veszpremi, T
Nguyen, Minh Tho #
Issue Date: 2001
Series Title: Physical Chemistry Chemical Physics vol:3 issue:9 pages:1588-1597
Conference: date:Univ Louvain, Dept Chem, B-3001 Louvain, Belgium; Budapest Univ Technol & Econ, Dept Inorgan Chem, H-1521 Budapest, Hungary; Vietnam Natl Univ, Coll Sci, Fac Chem, Hochiminh City, Vietnam
Abstract: Exploration of portions of the (C2NP) potential energy surface using both B3LYP and CCSD(T) methods with the 6-311++G(d,p) basis set, indicates that cyanophosphapropyne N=C-C=P is the most stable isomer, followed by isocyanophosphapropyne C=N-C=P, the linear azaphosphadicarbon C=C=N=P and the bent isocyanophosphavinylidene N=C-P=C. These higher-lying isomers are relatively stable with respect to unimolecular rearrangements and fragmentations. Their molecular properties including the geometries, rotational constants, vibrational wavenumbers, C-13 and P-31 NMR chemical shifts, heats of formation, excitation and ionisation energies, proton and electron affinities were determined. For the thermochemical quantities, CCSD(T) and EOM-CCSD computations with larger 6-311++G(3df,2p) and aug-cc-pVTZ basis sets were employed. It is remarkable that as a substituent, the phosphaethynyl -C=P moiety exerts a remarkably strong electron donor effect which markedly enhances the electron density and basicity of the attaching moieties. Thus, the proton affinities at N in NC-CP and at C in CN-CP are significantly increased thanks to the CP effect whereas those at C of CP are, as a consequence, strongly reduced.
ISSN: 1463-9076
Publication status: published
KU Leuven publication type: IT
Appears in Collections:Quantum Chemistry and Physical Chemistry Section
× corresponding author
# (joint) last author

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