NDLI: Do QTAIM metrics correlate with the strength of heavy element

Content Provider	World Health Organization (WHO)-Global Index Medicus
Author	Kaltsoyannis, Nikolas Mountain, Abigail R. E.
Description	Author Affiliation: Mountain AR ( Department of Chemistry, University College London, 20 Gordon Street, London WC1H 0AJ, UK.)
Abstract	The bonding in monomeric and dimeric molecular compounds of Cr, Mo, W and U is explored using the Quantum Theory of Atoms-in-Molecules (QTAIM). The metal–ligand and metal–metal bond critical point properties $ρ_{b},$ $∇^{2}ρ_{b}$ and $H_{b},$ and also the bond delocalisation indices δ(A, B), are correlated with the data from previous Ziegler–Rauk energy decomposition studies of the same systems. For $M_{2}X_{6}$ (M = Mo, W, U; X = Cl, F, OH, $NH_{2},$ $CH_{3}),$ $ρ_{b},$ $H_{b}$ and δ(A, B) display anticorrelations with the total interaction energy of the two $MX_{3}$ fragments, implying that the weaker metal–metal bonds (those between two uranium atoms) are the more covalent ones. By contrast, strongly positive correlations are observed between the QTAIM parameters and the energy decomposition orbital mixing energies. This is also the case for metal–carbon, metal–nitrogen and metal–oxygen bonds in $(CO)_{5}M–imidazole$ tautomers (M = Cr, Mo, W) and uranyl phosphinimine and phosphine oxide compounds. These targets were chosen specifically because their energy decompositions feature negligible net electrostatic + Pauli “pre-relaxation” effects, and the QTAIM parameters correlate strongly with the orbital mixing-dominated total interaction energies. The metal–metal bonds in $M_{2}X_{6}$ are found to have significantly positive $∇^{2}ρ_{b}$ (in agreement with many previous QTAIM studies of metal–metal bonding), and an anticorrelation is found between the total $X_{3}M–MX_{3}$ interaction energies and $∇^{2}ρ_{b}.$ The positive $∇^{2}ρ_{b}$ are traced to the dominant $λ_{3}$ principal curvature, which correlates well with the destabilising electronic kinetic energy density at the bond critical points, providing a rationalisation of the anticorrelation between the total $X_{3}M–MX_{3}$ interaction energies and $∇^{2}ρ_{b}.$
ISSN	14779226
Issue Number	37
Journal	Dalton Trans.
Volume Number	42
e-ISSN	13645447
Language	English
Publisher	Royal Society of Chemistry
Publisher Date	2013-10-07
Publisher Place	Great Britain (UK)
Access Restriction	Subscribed
Subject Keyword	Metals, Heavy Chemistry Organometallic Compounds Quantum Theory Ligands Molecular Structure Journal Article
Content Type	Text
Resource Type	Article
Subject	Inorganic Chemistry

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