Density functional theory (DFT) calculations were performed to examine the substituent effects on the interconversion of silabenzenes and their monocyclic non-aromatic isomers. A previous study suggested that aromaticity is the driving force for this process. Interestingly, our systematic calculations reveal that the contribution from aromaticity can be evaluated quantitatively (ca. 30 kcal mol-1). Thus it is the interplay of aromaticity and Bent's rule that determine their relative stabilities.

Aromaticity is one of the most important concepts in organic chemistry. A variety of metalla-aromatic compounds have been recently prepared and in most of those examples, the metal participates only in a monocyclic ring. In contrast, metal-bridged bicyclic aromatic molecules, in which a metal is shared between two aromatic rings, have been less developed. Herein, we report the first metal-bridged tricyclic aromatic system, in which the metal center is shared by three aromatic five-membered rings. These metalla-aromatics are formed by reaction between osmapentalyne and arene nucleophiles.

Antiaromatic compounds and small cyclic alkynes or carbynes are both challenging for synthetic chemists because of the destabilization caused by their antiaromaticity and highly distorted triple bonds, respectively. These dual destabilizations could be the reason why pentalyne (I), a highly antiaromatic and extremely strained cyclic alkyne, has never been synthesized.

Aromaticity, a highly stabilizing feature of molecules with delocalized electrons in closed circuits, is generally restricted to ‘Hückel’ systems with 4n+2 mobile electrons. Although the Möbius concept extends the principle of aromaticity to 4n mobile electron species, the rare known examples have complex, twisted topologies whose extension is unlikely. Here we report the realization of osmapentalenes, the first planar Möbius aromatic complexes with 16 and 18 valence electron transition metals.

Metallaaromatics have attracted continuing interest of both theoretical and experimental chemists since the first metallabenzene was predicted by Hoffmann and isolated by Roper. In sharp contrast to metallabenzenes, metallaphosphabenzene (MPB) is much less developed and has not been synthesized so far. Thus, developing synthetic approaches is urgent. Here we present thorough density functional theory (DFT) calculations on the thermodynamics and kinetics of the rearrangement between MPBs and the corresponding η5-phosphacyclopentadiene (η5-PCp) complexes.

A density functional theory study on olefins with five-membered monocyclic 4n and 4n+2 π-electron substituents (C4H3X; X=CH+, SiH+, BH, AlH, CH2, SiH2, O, S, NH, and CH−) was performed to assess the connection between the degree of substituent (anti)aromaticity and the profile of the lowest triplet-state (T1) potential-energy surface (PES) for twisting about olefinic CC bonds. It exploited both Hückel’s rule on aromaticity in the closed-shell singlet ground state (S0) and Baird’s rule on aromaticity in the lowest ππ* excited triplet state.

The many manifestations of aromaticity have long fascinated both experimentalists and theoreticians. Due to their degenerate half-filled MOs, triplet [n]annulenes with 4n π-electrons are also aromatic, but the degree of their stabilization has been difficult to quantify. The isomerization stabilization energy (ISE) method has been applied to evaluate the triplet aromaticity. The reliability of this approach is indicated by the strong correlation of the ISE results with NICS(1)zz, a magnetic indicator of triplet state aromaticity.

Density functional theory calculations (B3LYP) have been carried out to investigate the 4π-electron systems of 2,4-disila-1,3-diphosphacyclobutadiene (compound 1) and the tetrasilacyclobutadiene dication (compound 2). The calculated nucleus-independent chemical shift (NICS) values for these two compounds are negative, which indicates that the core rings of compounds 1 and 2 have a certain amount of aromaticity.