TY - JOUR
T1 - A combined QTAIM/IRI topological analysis of the effect of axial/equatorial positions of NH2 and CN substituents in the [(PY5Me2)MoO]+ complex
AU - Kenouche, Samir
AU - Martínez-Araya, Jorge I.
N1 - Publisher Copyright:
© 2022 Elsevier Inc.
PY - 2022/11
Y1 - 2022/11
N2 - By means of the Interaction Region Indicator (IRI) and Quantum Theory of Atoms in Molecules (QTAIM), the influence exerted by NH2 (amino) and CN (cyano) as electron donor and electron acceptor substituent groups, respectively, located at para–positions of axial and equatorial pyridine rings of derivatized complexes coming from the [(PY5Me2)MoO]+ complex during the hydrogen molecular release in the gas phase was analyzed. In any case, a H–H covalent bond is forming at the transition state, with a strengthening of the electron density of 5.5% when the substituent group involved is NH2 at the para–position of the axial pyridine ring. However, there was no difference between NH2 and CN when these substituent groups are located at the para–positions of the equatorial pyridine rings. The topological properties of electron densities from the QTAIM are not perturbed by the electron donor and electron acceptor nature of the substituents, even when these substituent groups are located at the axial or equatorial pyridine rings of the Mo–based complex.
AB - By means of the Interaction Region Indicator (IRI) and Quantum Theory of Atoms in Molecules (QTAIM), the influence exerted by NH2 (amino) and CN (cyano) as electron donor and electron acceptor substituent groups, respectively, located at para–positions of axial and equatorial pyridine rings of derivatized complexes coming from the [(PY5Me2)MoO]+ complex during the hydrogen molecular release in the gas phase was analyzed. In any case, a H–H covalent bond is forming at the transition state, with a strengthening of the electron density of 5.5% when the substituent group involved is NH2 at the para–position of the axial pyridine ring. However, there was no difference between NH2 and CN when these substituent groups are located at the para–positions of the equatorial pyridine rings. The topological properties of electron densities from the QTAIM are not perturbed by the electron donor and electron acceptor nature of the substituents, even when these substituent groups are located at the axial or equatorial pyridine rings of the Mo–based complex.
KW - Electron acceptor substituent group
KW - Electron donor substituent group
KW - IRI
KW - Molecular hydrogen release
KW - Mo–based complexes
KW - QTAIM
UR - http://www.scopus.com/inward/record.url?scp=85135306039&partnerID=8YFLogxK
U2 - 10.1016/j.jmgm.2022.108273
DO - 10.1016/j.jmgm.2022.108273
M3 - Article
C2 - 35930821
AN - SCOPUS:85135306039
SN - 1093-3263
VL - 116
JO - Journal of Molecular Graphics and Modelling
JF - Journal of Molecular Graphics and Modelling
M1 - 108273
ER -