Are Metallacyclopentadienes Always Non-Aromatic?

Even though metallacyclopentadienes (MCPs) are among the most common metallacycles, their electron delocalization (aromaticity) has received far less attention than other metallacycles, such as metallabenzenes. We systematically studied the aromaticity of MCPs with energetic (isomerization stabilization energy), density (delocalization index) and magnetic (current density) aromaticity indices. The indices agree that metallacyclopentadienes are, in general, weakly aromatic at most. The 18e− complexes showed the expected weak aromaticity, and only the d8 molecules are somewhat anti-aromatic. However, the theoretical account of the aromaticity of the 16e− MCPs is more convoluted. We find that the aromatic criteria for a 16e−d4 ruthenacyclopentadiene disagree. The lack of agreement shows that significant electron delocalization is not always related to great stability or to strong diatropic currents.

Revitalizing the Concept of Bond Order Through Delocalization Measures in Real Space

Ab initio quantum chemistry is an independent source of information supplying an ever widening group of experimental chemists. However, bridging the gap between these ab initio data and chemical insight remains a challenge. In particular, there is a need for a bond order index that characterizes novel bonding patterns in a reliable manner, while recovering the familiar effects occurring in well-known bonds. In this article, through a large body of calculations, we show how the delocalization index derived from Quantum Chemical Topology (QCT) serves as such a bond order. This index is defined in a parameter-free, intuitive and consistent manner, and with little qualitative dependency on the level of theory used. The delocalization index is also able to detect the subtler bonding effects that underpin most practical organic and inorganic chemistry. We explore and connect the properties of this index and open the door for its extensive usage in the understanding and discovery of novel chemistry.

Revitalizing the Concept of Bond Order Through Delocalization Measures in Real Space

Ab initio quantum chemistry is an independent source of information supplying an ever widening group of experimental chemists. However, bridging the gap between these ab initio data and chemical insight remains a challenge. In particular, there is a need for a bond order index that characterizes novel bonding patterns in a reliable manner, while recovering the familiar effects occurring in well-known bonds. In this article, through a large body of calculations, we show how the delocalization index derived from Quantum Chemical Topology (QCT) serves as such a bond order. This index is defined in a parameter-free, intuitive and consistent manner, and with little qualitative dependency on the level of theory used. The delocalization index is also able to detect the subtler bonding effects that underpin most practical organic and inorganic chemistry. We explore and connect the properties of this index and open the door for its extensive usage in the understanding and discovery of novel chemistry.

Multi-center covalency: revisiting the nature of anion–π interactions

Plot of the delocalization index, δ(X−,Ω), scaled by the internuclear distance, RX,Ω, versus the exchange–correlation potential energy, VXC(X−,Ω), for anion–π complexes.