Journal ArticleDOI
The QTAIM approach to chemical bonding between transition metals and carbocyclic rings: a combined experimental and theoretical study of (η5-C5H5)Mn(CO)3, (η6-C6H6)Cr(CO)3, and (E)-{(η5-C5H4)CF=CF(η5- C5H4)}(η5-C5H5)2Fe2
TLDR
The QTAIM indicators clearly demonstrate that for the n-hapto (eta(n)-C(n)H(n))M unit, there is generally a very similar level of chemical bonding for all M-C(ring) interactions, as expected on the basis of chemical experience.Abstract:
Experimental charge densities for (C5H5)Mn(CO)3 (2), (η6-C6H6)Cr(CO)3 (3), and (E)-{(η5-C5H4)CF═CF(η5-C5H4)}(η5-C5H5)2Fe2 (4) have been obtained by multipole refinement of high-resolution X-ray diffraction data at 100 K. The resultant densities were analyzed using the quantum theory of atoms in molecules (QTAIM). The electronic structures of these and related π-hydrocarbyl complexes have also been studied by ab initio density functional theory calculations, and a generally good agreement between theory and experiment with respect to the topological parameters was observed. The topological parameters indicate significant metal−ring covalency. A consistent area of disagreement concerns the topology of the metal−ring interactions. It is shown that because of the shared-shell bonding between the metal and the ring carbons, an annulus of very flat density ρ and very small ▽ρ is formed, which leads to topologically unstable structures close to catastrophe points. This in turn leads to unpredictable numbers of m...read more
Citations
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Journal ArticleDOI
Does covalency increase or decrease across the actinide series? Implications for minor actinide partitioning.
TL;DR: It is suggested that care must be taken when using quantum chemistry to assess metal-ligand covalency in this part of the periodic table and also topological analysis of the electron density via the quantum theory of atoms-in-molecules.
Journal ArticleDOI
Bonding in Endohedral Metallofullerenes as Studied by Quantum Theory of Atoms in Molecules
TL;DR: Analysis of the delocalization indices and bond critical point (BCP) indicators revealed that all types of bonding in EMFs exhibit a high degree of covalency, and the ionic model is reasonable only for the Ca-based EMFs.
Journal ArticleDOI
Halogen Bonding: A Halogen-Centered Noncovalent Interaction Yet to Be Understood
TL;DR: In this article, the Independent Gradient Model (IGM) was used for probing strong and weak halogen-assisted noncovalent interactions in molecular domains, especially in the weak bonding regime.
Journal ArticleDOI
Topological analysis of the metal-metal bond: A tutorial review
Christine Lepetit,Christine Lepetit,Pierre Fau,Pierre Fau,Katia Fajerwerg,Katia Fajerwerg,Myrtil L. Kahn,Myrtil L. Kahn,Bernard Silvi +8 more
TL;DR: In this paper, the topological methods of analysis of the electron density and related functions such as the electron localization function (ELF) and the electron localizability indicator (ELI-D) enable the theoretical characterization of various metal-metal (M-M) bonds.
Journal ArticleDOI
Dispersion Makes the Difference: Bisligated Transition States Found for the Oxidative Addition of Pd(PtBu3)2 to Ar-OSO2R and Dispersion-Controlled Chemoselectivity in Reactions with Pd[P(iPr)(tBu2)]2
TL;DR: The manipulation of the steric nature of ligands is a key design principle in organometallic reactivity as mentioned in this paper, and while general intuition assumes steric effects to be repulsive, recent reports counter-intuit...
References
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Journal ArticleDOI
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