In this review, we provide a consistent description of noncovalent interactions, covering most groups of the Periodic Table. Different types of bonds are discussed using their trivial names. Moreover, the new name “Spodium bonds” is proposed for group 12 since noncovalent interactions involving this group of elements as electron acceptors have not yet been named. Excluding hydrogen bonds, the following noncovalent interactions will be discussed: alkali, alkaline earth, regium, spodium, triel, tetrel, pnictogen, chalcogen, halogen, and aerogen, which almost covers the Periodic Table entirely. Other interactions, such as orthogonal interactions and π-π stacking, will also be considered. Research and applications of σ-hole and π-hole interactions involving the p-block element is growing exponentially. The important applications include supramolecular chemistry, crystal engineering, catalysis, enzymatic chemistry molecular machines, membrane ion transport, etc. Despite the fact that this review is not intended to be comprehensive, a number of representative works for each type of interaction is provided. The possibility of modeling the dissociation energies of the complexes using different models (HSAB, ECW, Alkorta-Legon) was analyzed. Finally, the extension of Cahn-Ingold-Prelog priority rules to noncovalent is proposed.

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Not Only Hydrogen Bonds: Other Noncovalent Interactions

https://chemistry-europe.onlinelibrary.wiley.com/doi/pdf/10.1002/ejoc.202000660

σ-Hole Interactions in Catalysis

The term spodium (Sp) bond is proposed to refer to a net attractive interaction between any element of Group 12 and electron-rich atoms (Lewis bases or anions). These noncovalent interactions are markedly different from coordination bonds (antibonding Sp-ligand orbital involved). Evidence is provided for the existence of this interaction by calculations at the RI-MP2/aug-cc-pVTZ level of theory, atoms-in-molecules, and natural bond orbital analyses and by examining solid-state structures in the Cambridge Structure Database.

Spodium Bonds: Noncovalent Interactions Involving Group 12 Elements.

Pnictogen bonding in coordination chemistry

The tetrel bond (TB) recruits an element drawn from the C, Si, Ge, Sn, Pb family as electron acceptor in an interaction with a partner Lewis base. The underlying principles that explain this attractive interaction are described in terms of occupied and vacant orbitals, total electron density, and electrostatic potential. These principles facilitate a delineation of the factors that feed into a strong TB. The geometric deformation that occurs within the tetrel-bearing Lewis acid monomer is a particularly important issue, with both primary and secondary effects. As a first-row atom of low polarizability, C is a reluctant participant in TBs, but its preponderance in organic and biochemistry make it extremely important that its potential in this regard be thoroughly understood. The IR and NMR manifestations of tetrel bonding are explored as spectroscopy offers a bridge to experimental examination of this phenomenon. In addition to the most common σ-hole type TBs, discussion is provided of π-hole interactions which are a result of a common alternate covalent bonding pattern of tetrel atoms.

Origins and properties of the tetrel bond

Some cases of close contacts involving rhenium of perrhenate esters are presented and investigated computationally. The structures and calculated interaction energies confirm the attractiveness of these contacts, which display geometries typical of σ-hole interactions. The short Re···O contacts observed in three crystalline perrhenate salts confirm the general ability of rhenium compounds, both neutral and ionic, to form such interactions. 

σ-Hole Interactions Involving a Group 7 Metal: Close Contacts in Neutral and Anionic Rhenium Derivatives

Benchmark Rotor Dynamics and Light-Driven Motors Engineered in 3D Porous Architectures

C(sp3) atoms are known to act as electrophilic sites in self-assembly processes, and in all cases reported till now, they form only one interaction with nucleophiles; that is, they function as monodentate tetrel bond donors. This manuscript reports experimental (X-ray structural analysis) and theoretical evidence (DFT calculations), proving that the methylene carbon in bis-pyridinium methylene salts establishes two short and directional C(sp3)···anion interactions; that is, they function as bidentate tetrel bond donors.

https://pubs.acs.org/doi/pdf/10.1021/acs.cgd.2c01386

Andrea Daolio

Papers

σ-Hole Interactions Involving a Group 7 Metal: Close Contacts in Neutral and Anionic Rhenium Derivatives

Benchmark Rotor Dynamics and Light-Driven Motors Engineered in 3D Porous Architectures

Geminal Charge-Assisted Tetrel Bonds in Bis-Pyridinium Methylene Salts

Ultra-fast rotor dynamics and gas reorientation in crystalline nanoporous architectures

Chalcogen bond in bioactive compounds