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The Ru PR 3 bonds of 1 – 2 ( a - b )- PC , Ru CHPh bonds of 1a - b , 2 - Inact / Act and 1a - b , 2 - RCB were analyzed by charge decomposition (CDA) and natural bond orbital (NBO). We have found that the dissociation step of the Ru PR 3 bond is driven by charge transfer, while the RCB by polarization effects. Furthermore, the π(C ipso )–π*(Ru C) interaction was associated with delocalization effects in the benzylidene ring. Likewise, the nature of the rotameric changes in the carbene was studied through the resonance stabilization energy ( E NLW ). 2 presented a lower Δ E NLW (Inactive → Active) than 1a - b , which confirms that the delocalization effects are related to a low carbene rotameric energy. [ABSTRACT FROM AUTHOR]

Abstract: Nucleophilicity and elecrophilicity of mono and disubstituted silylenes are analyzed using the molecular electrostatic potential and the dual descriptor , defined within the so called conceptual DFT. A set of 32 compounds has been chosen which can be classified into 4 groups or families based on a linear relationship between the molecular electrostatic potential measured in the electrophilic (empty 3 orbital) and nucleophilic (lone pair) regions around of the silicon atom. The electrophilic and nucleophilic character of silylenes given by is connected to the orbital-resolved dual descriptor through the -electron donating property of the substituent. [Copyright &y& Elsevier]

Abstract: We have explored the relationships between the reaction force F(ξ), the reaction force constant κ(ξ) and the projected force constants of the intramolecular proton transfer HO−Nsp="0.25" />→OSH along the intrinsic reaction coordinate ξ. The structural changes and energetics associated with the reaction are analyzed in terms of the three regions defined by F(ξ): reactant, transition and product. The significance of the similarity between κ(ξ) and the variation of the force constant associated to the reaction coordinate mode, kξ (ξ), is discussed in detail. [Copyright &y& Elsevier]

Abstract: The average local ionization energy and the Fukui function f(r) are conceptually-independent measures of molecular reactive behavior. In this Letter, we use Janak’s theorem to establish a plausible link between and f(r). In particular, both can generally be expected to identify the same sites as most reactive toward electrophiles. [Copyright &y& Elsevier]

Highlights: [•] We analyzed the PES of Si10Li8 including planar and three-dimensional structures. [•] The most stable isomer over Si10Li8 PES is a three-dimensional structure. [•] The structure is stabilized by electrostatic interactions between its fragments. [•] The polarizability values correlate in good order with the relative stability. [Copyright &y& Elsevier]