Charge-Shift Bonding: A New and Unique Form of Bonding.

Charge-shift bonds (CSB) constitute a new class of bonds different than covalent/polar-covalent and ionic-bonds. Bonding in CSB is not contributed by either the covalent or the ionic structures of the bond, but rather by the resonance interaction between the structures. This essay describes the reasons why the CSB family was overlooked by valence-bond pioneers (Textbox 1). It then demonstrates that the unique status of CSBs is not theory-dependent. Thus, Valence-bond (VB), molecular-orbital (MO),[21,22] and Energy-Decomposition-Analysis (EDA)[23], as well as a variety of electron-density theories; Electron-Localization Function (ELF),[27] Quantum Thery of Atoms in Molecules (QTAIM),[24] and Electron-Stress Tensor (EST) approaches;[25,26] all these show the distinction of CSB vis-à-vis covalent and ionic bonds. Furthermore, the covalent-ionic resonance energy can be quantified from experiment, and hence having the same essential status as resonance energies of organic molecules, e.g., benzene. The essay then demonstrates how a variety of bond types -- dative-bonds, coordinative-bonds, and hypervalent-bonds, including 3-electron-bonds -- are CSBs. Subsequently, some experimental manifestations of CSBs are discussed, including recent experimental articulations of the concept.[78,81,82] The essay ends by arguing that the definition of CSB as a distinct family of bonding fulfills the necessary conditions for making such a claim. The distinction  between covalent-bonds and CSBs is thus fundamental, with a potential to bring about a Renaissance in the mental-map of the chemical bond, and to contribute to productive chemical diversity.

• Publication year

  2019

• Venue

  Angewandte Chemie

• Publication date

  2019-11-12

• Fields of study

  Medicine, Chemistry

• Identifiers
  DOI 10.1002/anie.201910085PMID 31476104
• External record

  Open on Semantic Scholar

• Source metadata

  Semantic Scholar, PubMed

• No claims are published for this paper.

• No concepts are published for this paper.

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