Analysis of Hückel's [4n + 2] rule through electronic delocalization measures

In the present work, we analyze the pi-electronic delocalization in a series of annulenes and their dications and dianions by using electron delocalization indices calculated in the framework of the quantum theory of atoms in molecules. The aim of our study is to discuss the Hückel's 4n + 2 rule from the viewpoint of pi-electronic delocalization. Our results show that there is an important increase of electronic delocalization (of about 1 e) when going from antiaromatic 4n pi systems to aromatic (4n + 2)pi systems. Less clear is the change in pi-electronic delocalization when we move from a (4n + 2)pi-aromatic to a 4n pi-antiaromatic species by adding or removing a pair of electrons.     

New ruthenium(II) complexes with enantiomerically pure bis- and tris(pinene)-fused tridentate ligands. Synthesis, characterization and stereoisomeric analysis

A new set of Ru-Cl complexes containing either the pinene[5,6]bpea ligand (L1) or the C3 symmetric pinene[4,5]tpmOMe (L2) tridentate ligand in combination with the bidentate (B) 2,2'-bipyridine (bpy) or 1,2-diphenylphosphinoethane (dppe) with general formula [RuCl(L1 or L2)(B)](+) have been prepared and thoroughly characterized. In the solid state, X-ray diffraction analysis techniques have been used. In solution, cyclic voltammetry (CV) and 1D and 2D NMR spectroscopy have been employed. DFT calculations have been also performed on these complexes and their achiral analogues previously reported in our group, to interpret and complement experimental results. Whereas isomerically pure complexes ([Ru(II)Cl(L2)(bpy)](BF4), 5 and [Ru(II)Cl(L2)(dppe)](BF4), 6) are obtained when starting from the highly symmetric [Ru(III)Cl3(L2)], 2, isomeric mixtures of cis, fac-[Ru(II)Cl(L1)(bpy)](BF4) (3b/3b'), trans,fac- (3a) and up/down,mer- (3c, 3d) isomers are formed when bpy is added to the less symmetric [Ru(III)Cl3(L1)], 1, in contrast to the case of the bulky dppe ligand that, upon coordination to 1, leads to the trans,fac-[Ru(II)Cl(L1)(dppe)](BF4) (4a) complex as a sole isomer due to steric factors.     

Quantification of bromine in flame-retardant coatings by radiofrequency glow discharge–optical emission spectrometry

There is an increasing concern regarding the toxicity and environmental distribution and impact of brominated organic compounds employed as flame retardants. Thus, present interest in searching for new analytical techniques and methods allowing a rapid, simple and reliable detection of those compounds in materials and wastes potentially containing such flame retardants is not surprising. The feasibility of using radiofrequency glow discharge plasma spectrometry coupled with optical emission spectrometry (rf-GD-OES) as a rapid and simple tool to directly analyse bromine-containing flame-retardant polymeric layers is investigated here. Polymeric layers for calibration were made by mixing appropriate amounts of tetrabromobisphenol A, bisphenol A, phloroglucinol and diphenylmethane-4,4′-diisocyanate in tetrahydrofuran. The corresponding blanks (polymers without tetrabromobisphenol A) were also prepared. Detection of bromine was investigated both in the visible (at 470.48 nm) and in the near-infrared (at 827.24 nm) regions, using a charge-coupled device for detection. Discharge parameters affecting the emission intensity of bromine were first optimized (in argon and helium as possible plasma gases) and the analytical performance characteristics were then evaluated. The best detection limit (0.044% Br) was achieved measuring Br I 827.24 nm in a He discharge, using a forward power of 70 W and a pressure of 45 Torr. The linearity range extended up to 27% Br. Finally, the applicability of the rf-GD-OES method proposed to the quantitative analysis of bromine in solid materials coated with flame-retardant commercial paints was successfully demonstrated. Figure Flame Retardants     

Properties of aromaticity indices based on the one-electron density matrix

Proper normalization of two previously published indices yields aromaticity measures that, when computed within the Hückel molecular orbital (HMO) approximation, closely match the topological resonance energies per pi electron of aromatic annulenes and their ions. The normalized indices, which quantify aromaticity of individual rings in polycyclic systems, are equally applicable to homocyclic and heterocyclic compounds and can be readily computed from 1-matrices calculated at any level of electronic structure theory. However, only the index ING, derived from the Giambiagi formula, produces proper ordering of aromaticities of heterocyclic compounds, provided it is calculated from all-electron wavefunctions in conjunction with the atoms in molecule (AIM) partitioning. Its values are shown to be strongly affected by electron correlation effects. Because of its apparent inability to distinguish between anti- and nonaromatic systems, ING should only be employed for aromatic species.     

Table salt and other alkali metal chloride oligomers: structure, stability, and bonding

We have investigated table salt and other alkali metal chloride monomers, ClM, and (distorted) cubic tetramers, (ClM)(4), with M = Li, Na, K, and Rb, using density functional theory (DFT) at the BP86/TZ2P level. Our objectives are to determine how the structure and thermochemistry (e.g., Cl-M bond lengths and strengths, oligomerization energies, etc.) of alkali metal chlorides depend on the metal atom and to understand the emerging trends in terms of quantitative Kohn-Sham molecular orbital (KS-MO) theory. The analyses confirm the high polarity of the Cl-M bond (dipole moment, VDD, and Hirshfeld atomic charges). They also reveal that bond overlap derived stabilization (approximately -26, -20, and -8 kcal/mol), although clearly larger than in the corresponding F-M bonds, contributes relatively little to the (trend in) bond strengths (-105, -90, and -94 kcal/mol) along M = Li, Na, and K. Thus, the Cl-M bonding mechanism resembles more closely that of the even more ionic F-M bond than that of the more covalent C-M or H-M bonds. Tetramerization causes the Cl-M bond to expand, and it reduces its polarity.     

A model of the chemical bond must be rooted in quantum mechanics, provide insight, and possess predictive power

In this response to the preceding paper by Bader, we show that the core arguments and statements presented in the latter are flawed. We argue that it is insufficient for a model of the chemical bond to be rooted in quantum mechanics. A good model must in addition provide insight and possess predictive power. Our molecular orbital (MO) model of the chemical bond, in particular, the associated energy-decomposition approach satisfies all these conditions. On the other hand, Atoms-in-Molecules (AIM) theory is only rooted in quantum mechanics as far as its mathematical framework is concerned. The physical status of its central concepts is not so clear. In particular, "bond paths" and "bond critical points" are once more confirmed not to be indicators of a stabilizing interaction. Moreover, AIM theory lacks any predictive power. We also address specific questions raised in the preceding paper. Finally, interpreting chemical bonding implies choosing a perspective on this phenomenon. That there are many perspectives is a matter of fact and this is in no way unphysical. What is unscientific is to claim uniqueness and truth for one of these choices, namely AIM, and to dismiss on this ground all other approaches.     

Electron localization function at the correlated level

The electron localization function (ELF) has been proven so far a valuable tool to determine the location of electron pairs. Because of that, the ELF has been widely used to understand the nature of the chemical bonding and to discuss the mechanism of chemical reactions. Up to now, most applications of the ELF have been performed with monodeterminantal methods and only few attempts to calculate this function for correlated wave functions have been carried out. Here, a formulation of ELF valid for mono- and multiconfigurational wave functions is given and compared with previous recently reported approaches. The method described does not require the use of the homogeneous electron gas to define the ELF, at variance with the ELF definition given by Becke. The effect of the electron correlation in the ELF, introduced by means of configuration interaction with singles and doubles calculations, is discussed in the light of the results derived from a set of atomic and molecular systems.     

Analysis of electron delocalization in aromatic systems: individual molecular orbital contributions to para-delocalization indexes (PDI)

Our research group has recently defined two new aromaticity indexes based on the analysis of electron delocalization in aromatic species using the quantum theory of atoms-in-molecules. One of these indexes is the para-delocalization index (PDI) that measures the electronic delocalization between para-related carbon atoms in six-membered rings. In this paper, we show that this index can be partitioned into individual molecular orbital contributions. We have applied this PDI decomposition to several polycyclic aromatic hydrocarbons showing that this partitioning provides new insight into the origin of aromaticity.     

Interplay between intramolecular resonance-assisted hydrogen bonding and aromaticity in o-hydroxyaryl aldehydes

In this work, we analyze a series of o-hydroxyaryl aldehydes to discuss the interrelation between the resonance-assisted hydrogen bond (RAHB) formation and the aromaticity of the adjacent aromatic rings. As compared to the nonaromatic reference species (malonaldehyde), the studied compounds can be separated into two groups: first, the set of systems that have a stronger RAHB than that of the reference species, for which there is a Kekulé structure with a localized double CC bond linking substituted carbon atoms; and second, the systems having a weaker RAHB than that of the reference species, for which only pi-electrons coming from a localized Clar pi-sextet can be involved in the RAHB. As to aromaticity, there is a clear reduction of aromaticity in the substituted ipso ring for the former group of systems due to the formation of the RAHB, while for the latter group of species only a slight change of local aromaticity is observed in the substituted ipso ring.