dc.contributor.author |
Landman, Marile
|
|
dc.contributor.author |
Conradie, Jeanet
|
|
dc.date.accessioned |
2015-05-29T06:00:22Z |
|
dc.date.available |
2015-05-29T06:00:22Z |
|
dc.date.issued |
2015-08 |
|
dc.description.abstract |
A density functional theory (DFT) calculated conformation analysis of the twelve possible conformations
of [Mo(CO)4(PPh3){C(NHCy)(2-furyl)}], 1, utilizing different DFT methods, showed that both the cis-syn,Z
(2), 1-Z, and the cis-syn,Z (2), 1-E, conformations of this aminocarbene complex have similar electronic
and Gibbs free energies. The solid-state crystal structure of the 1-Z is presented in this study and compared
to the structure of the 1-E conformation. The stability of 1-Z, versus the previously published
solid-state structure of conformer 1-E, is ascribed to stabilization of the NAH OFu intramolecular bond.
This is evidenced by a shorter H O intramolecular bond in the experimental crystal structure of 1-Z. The
stability of the 1-Z and 1-E conformations were analyzed and compared by density functional theory,
quantum theory of atoms in molecules (QTAIM) and natural bond orbital (NBO) methods. The NBO
analysis reveals similar but stronger donor–acceptor interactions in 1-Z than in 1-E. QTAIM calculations
indicate 6 and 5 bond critical points related to intramolecular bonds stabilizing the orientation of 2-furyl
and NHCy in 1-Z and 1-E respectively. |
en_ZA |
dc.description.embargo |
2016-08-30 |
en_ZA |
dc.description.librarian |
hb2015 |
en_ZA |
dc.description.sponsorship |
Norwegian Supercomputing Program (NOTUR) through a grant of computer
time (Grant No. NN4654K).The South African National Research Foundation, HPC Warehouse Facility.The Central Research Fund of the University of the Free State,
Bloemfontein and the University of Pretoria. |
en_ZA |
dc.description.uri |
http://www.elsevier.com/locate/molstruc |
en_ZA |
dc.identifier.citation |
Landman, M & Conradie, J 2015, 'E versus Z isomers of Fischer aminocarbene complex [Mo(CO)4(PPh3){C(NHCy)(2-furyl)}] : NH⋯O versus CH⋯O intramolecular hydrogen bonds', Journal of Molecular Structure, vol. 1094, pp. 36-45. |
en_ZA |
dc.identifier.issn |
0022-2860 (print) |
|
dc.identifier.issn |
1872-8014 (online) |
|
dc.identifier.other |
10.1016/j.molstruc.2015.04.001 |
|
dc.identifier.uri |
http://hdl.handle.net/2263/45336 |
|
dc.language.iso |
en |
en_ZA |
dc.publisher |
Elsevier |
en_ZA |
dc.rights |
© 2015 Elsevier B.V. All rights reserved. Notice : this is the author’s version of a work that was accepted for publication in Journal of Molecular Structure. Changes resulting from the publishing process, such as peer review, editing, corrections, structural formatting, and other quality control mechanisms may not be reflected in this document. Changes may have been made to this work since it was submitted for publication. A definitive version was subsequently published in Journal of Molecular Structure, vol. 1094, pp. 36-45, 2015. doi :10.1016/j.molstruc.2015.04.001 |
en_ZA |
dc.subject |
Fischer carbene |
en_ZA |
dc.subject |
Molybdenum |
en_ZA |
dc.subject |
NBO analysis |
en_ZA |
dc.subject |
Hydrogen bond |
en_ZA |
dc.subject |
Density functional theory (DFT) |
en_ZA |
dc.subject |
Natural bond orbital (NBO) |
en_ZA |
dc.subject |
Quantum theory of atoms in molecules (QTAIM) |
en_ZA |
dc.title |
E versus Z isomers of Fischer aminocarbene complex [Mo(CO)4(PPh3){C(NHCy)(2-furyl)}] : Nsingle bondH⋯O versus Csingle bondH⋯O intramolecular hydrogen bonds |
en_ZA |
dc.type |
Postprint Article |
en_ZA |