Aromaticity in metallabenzenes

The electronic structure and bonding situation in 21 metallabenzenes (metal=Os, Ru, Ir, Rh, Pt, and Pd) were investigated at the DFT level (BP86/TZ2P) by using an energy decomposition analysis (EDA) of the interaction energy between various fragments. The aim of the work is to estimate the strength of the pi bonding and the aromatic character of the metallacyclic compounds. Analysis of the electronic structure shows that the metallacyclic moiety has five occupied pi orbitals, two with b1 symmetry and three with a2 symmetry, which describe the pi-bonding interactions. The metallabenzenes are thus 10 pi-electron systems. This holds for 16-electron and for 18-electron complexes. The pi bonding in the metallabenzenes results mainly from the b1 contribution, but the a2 contribution is not negligible. Comparison of the pi-bonding strength in the metallacyclic compounds with acylic reference molecules indicates that metallabenzenes should be considered as aromatic compounds whose extra stabilization due to aromatic conjugation is weaker than in benzene. The calculated aromatic stabilization energies (ASEs) are between 8.7 kcal mol(-1) for 13 and 37.6 kcal mol(-1) for 16 which is nearly as aromatic as benzene (ASE=42.5 kcal mol(-1)). The classical metallabenzene model compounds 1 and 4 exhibit intermediate aromaticity with ASE values of 33.4 and 17.6 kcal mol(-1). The greater stability of the 5d complexes compared with the 4d species appears not to be related to the strength of pi conjugation. From the data reported here there is no apparent trend or pattern which indicates a correlation between aromatic stabilization and particular ligands, metals, coordination numbers or charge. The lower metal-C5H5 binding energy of the 4d complexes correlates rather with weaker sigma-orbital interactions.     

Aromaticity Switching in Porphyrinoids

The aromaticity of porphyrinoids can be substantially altered by reversible modification of their original electronic structures. Well‐defined modulators can be used as a means to initiate these modifications, including redox processes, acid–base chemistry, and conformational phenomena. This Focus Review emphasizes the situation for which a single macrocyclic frame alternatively adopts diatropic and paratropic features and both situations are readily and mutually exchangeable. Eventually, such a porphyrinoid transformation can be explored as a suitable element to construct switchable optoelectronic materials.     

Aromaticity in cyclic alkali clusters

Density functional calculations on a hexagonal 1D sodium cluster and a 2D potassium cluster show that the M6 (M = Na, K) rings in the chain present in 3D [Na2MoO3L(H2O)2]n (1) and 2D [K2MoO3L(H2O)3]n (2) are aromatic in character according to the nucleus independent chemical shift (NICS) and multicenter bond indices (MCI) values. The NICS values at the center of the Na6 rings and at the cage center of the K6 rings are comparable to the corresponding values of their polyacene analogues in most cases. The stability and reactivity patterns of the M6 rings also follow a similar trend as their organic analogues.     

Aromaticity and curvature in heteroacepentalenes

Heteroatom-substituted acepentalene derivatives which are isoelectronic with the known acepentalenediide dianion are nonplanar, fused aromatic tricycles which are hemifullerenes of the corresponding C20 heteroanalogue. Depending on the number and position of heteroatoms, they may be anionic, neutral, or cationic. A nucleus-independent chemical shift study indicates that substitution of the central carbon of the acepentalenediide system with N or O results in a substantial increase in aromaticity. Peripheral aza substitution on the other hand tends to increase curvature and decrease aromaticity. Alkylation or protonation at the central position of asymmetrically substituted heteroacepentalenides leads to chiral, bowl-shaped, 10 pi aromatic species.     

Aromaticity of corazulenic fullerenes

A novel class of non-classical fullerenes, having pentagon–heptagon pairs, as in azulene, is modeled. The various coverings, sometimes alternating azulenic and benzenic units, are designed by some new sequences of map operations or generalized operations. The hypothetical azulenic fullerenes are characterized by PM3 semiempirical data and POAV1 strain energy SE. Their aromaticity is discussed in the light of several criteria. The HOMA index of aromaticity enabled evaluation of global and local aromaticity of the designed fullerenes.     

Aromaticity as a Quantitative Concept. 6. Aromaticity Variation with Molecular Environment

The classical aromaticity of most heterocycles, and of some carbocycles such as azulene, increases with the polarity of the medium as shown by experimental and calculated bond lengths, aromaticity indices, and dipole moments.     

Aromaticity of carbon nanotubes

Carbon nanotubes are composed of cylindrical graphite sheets. Both nanotubes and graphite sheets are benzenoid derivatives composed of sp2 carbon atoms arranged in a hexagonal pattern. Therefore both systems are aromatic. The extent of the aromatic character of a molecule G (here benzenoids) can be explained in terms of the number of possible Kekulé structures in G. In this work the Kekulé structures in carbon nanotubes and the corresponding, rectangular, graphite-sheets the tubes might originate from, were enumerated. It was shown that (2,2), (3,3), and (4,4) carbon nanotubes are more aromatic than the corresponding, rectangular, planar structures. This explains why it might be more difficult to saturate nanotubes by addition reactions than the respective, "narrow", graphite sheets.     

Aromaticity and antiaromaticity in transition-metal systems

Aromaticity is an important concept in chemistry primarily for organic compounds, but it has been extended to compounds containing transition-metal atoms. Recent findings of aromaticity and antiaromaticity in all-metal clusters have stimulated further research in describing the chemical bonding, structures and stability in transition-metal clusters and compounds on the basis of aromaticity and antiaromaticity, which are reviewed here. The presence of d-orbitals endows much more diverse chemistry, structure and chemical bonding to transition-metal clusters and compounds. One interesting feature is the existence of a new type of aromaticity-delta-aromaticity, in addition to sigma- and pi-aromaticity which are the only possible types for main-group compounds. Another striking characteristic in the chemical bonding of transition-metal systems is the multi-fold nature of aromaticity, antiaromaticity or even conflicting aromaticity. Separate sets of counting rules have been proposed for cyclic transition-metal systems to account for the three types of sigma-, pi- and delta-aromaticity/antiaromaticity. The diverse transition-metal clusters and compounds reviewed here indicate that multiple aromaticity and antiaromaticity may be much more common in chemistry than one would anticipate. It is hoped that the current review will stimulate interest in further understanding the structure and bonding, on the basis of aromaticity and antiaromaticity, of other known or unknown transition-metal systems, such as the active sites of enzymes or other biomolecules which contain transition-metal atoms and clusters.     

Aromaticity and Pericyclic Reactions

Pericyclic reactions formally resemble the conversion of one Kekulé structure into another; the transition state may be “aromatic”, “nonaromatic”, or “antiaromatic”. Thermally induced pericyclic reactions proceed preferentially via aromatic transition states whereas their photochemical counterparts lead to products that are formed via antiaromatic transition states.     

多环化合物的芳香性

介绍了简单判断多环化合物的芳香性、非芳香性、反芳香性、同芳香性及反同芳香性的方法及其在有机化学中的应用.     

Aromaticity and Stability of Azaborines

The influence of the relative boron and nitrogen positions on aromaticity of the three isomeric 1,2‐, 1,3‐, and 1,4‐azaborines has been investigated by computing the extra cyclic resonance energy, NICS(0)_πzz index and by visualizing the π‐electron (de)shielding pattern as a response of the π system to a perpendicular magnetic field. The origin of the known stability trend, in which the 1,2‐/1,3‐isomer is the most/least stable, was examined by using an isomerization energy decomposition analysis. The 1,3‐arrangement of B and N atoms creates a charge separation in the π‐electron system, which was found to be responsible for the lowest stability of 1,3‐azaborine. This charge separation can, in turn, be considered as a driving force for the strongest cyclic π‐electron delocalization, making this same isomer the most aromatic. Despite the well‐known fact that the B?N bond attenuates electron delocalization due to large electronegativity difference between the atoms, the 1,4‐B,N relationship reduces aromaticity to a greater extent by making the π‐electron delocalization more one‐directional (from N to B) than cyclic. Thus, 1,4‐azaborine was found to be the least aromatic. Its lower stability with respect to the 1,2‐isomer was explained by the larger exchange repulsion.     

关于芳香性的概念

简要介绍了芳香性概念的发展历史 ,并从结构、稳定性、反应性能等方面进行了总结     

Aromaticity and Diatropicity of Polyacenequinododimethides

Typical polyacenequinododimethides exist only in a single classical structure. These hydrocarbons are moderately aromatic and diatropic, although they have no aromatic conjugated circuits. This apparent dichotomy was resolved with our graph theory of aromaticity and magnetotropicity. Many nonconjugated circuits were found to contribute collectively to aromaticity and diatropicity. For individual molecules, local aromaticity increases with distance from the exo‐methylene groups. This fact indicates that the conjugated‐circuit model is not always applicable to semibenzenoid hydrocarbons such as polyacenequinododimethides.     

Aromaticity under star dust conditions

Astronomical observations have revealed diffuse interstellar bands ranging from blue in the visible spectrum to the near IR. It has been suggested that these bands exist, owing to the presence of polyaromatic hydrocarbons or fullerene in the vicinity of certain stars, and constitute residual material from stellar explosions. The intention here is to study the relative stability of these species, when exposed to extreme conditions. The aromaticity of polycarbon molecules is an important aspect of this explanation.     

芳香性研究进展

综述了芳香性的概念,芳香性的判据和应用以及研究进展,随着量子理论和合成新的芳香环的迅速发展,芳香性含意也在深化和发展,芳香族化合物的应用范围日益扩大。     

Aromaticity in transition metal oxide structures.

The concept of aromaticity is useful for understanding the properties of some polyoxometalates containing transition metals such as vanadium, molybdenum, and tungsten having structures based on metal macropolygons and macropolyhedra with M-O-M edges. Thus, the aromatic macrocuboctahedral Keggin ions readily undergo one-electron reductions to highly colored mixed-valence "blues" (e.g., molybdenum blue), whereas the macroicosahedral Silverton ions, M(IV)Mo12O42(8-) (M(IV) = Ce, Th, U), which, like cyclohexane, do not have vertex valence orbitals available for delocalization, do not undergo analogous reduction reactions. A macrohexagon of d1 vanadium(IV) atoms as V-O-V units has been imbedded into an electronically inactive borate matrix in the ion [V6B20O50H8](8-). The small beta unit for the V-O-V interactions in this V6 macrohexagon leads to an unprecedented example of high spin aromaticity with a paramagnetism corresponding to four unpaired electrons per V6 unit in contrast to benzene, which is diamagnetic and hence exhibits low spin aromaticity. The M-O-M interactions in these aromatic metal oxides are closely related to the Cu-O-Cu interactions in the high critical temperature superconducting copper oxides which are essential to the electron transport in these systems.     

全金属负离子团簇Ga42-、In42-芳香性的磁特征与多重芳香性

The optimized geometries, frequencies, and total electronic energies of two all-metal dianionic clusters Ga42- , In42- are calculated at the B3LYP, B3PW91, and MP2 levels of theory. There are two stable structures for each Ga42- , In42- species. For Ga42- , In42- species the square isomers are the most stable. On the basis of these computed stable structures we focus on two magnetic properties: magnetic susceptibility anisotropy and nucleus-independent chemical shift (NICS) for the square planar Ga42- , In42- isomers, which are calculated with B3LYP and HF methods. The computed results of NICS show that the square planar Ga42- , In42- isomers possess strong aromaticity. The detailed molecular orbital analysis for the two isomers further reveals that the two square planar Ga42- , In42- isomers have multiple-fold aromaticity: one delocalized π MOs and two delocalized σ MOs, which play important role in explaining the special stability of these all-metal square clusters.