Carboranes as lewis acids: Tetrel bonding in CB11H11 carbonium ylide

High-level quantum-chemical computations (G4MP2) are carried out in the study of complexes featuring tetrel bonding between the carbon atom in the carbenoid CBH-obtained by hydride removal in the C-H bond of the known closo-monocarbadodecaborate anion CBH (-) and acting as Lewis acid (LA)-and Lewis...

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Detalles Bibliográficos
Autores: Ferrer, Maxime, Alkorta, Ibon, Elguero, José, Oliva, José M.
Tipo de recurso: artículo
Estado:Versión publicada
Fecha de publicación:2021
País:España
Institución:Consejo Superior de Investigaciones Científicas (CSIC)
Repositorio:DIGITAL.CSIC. Repositorio Institucional del CSIC
OAI Identifier:oai:digital.csic.es:10261/252573
Acceso en línea:http://hdl.handle.net/10261/252573
Access Level:acceso abierto
Palabra clave:Lewis acid
Carborane
carbonium ylide
Tetrel bond
Quantum chemistry
Electron density
ELF
Descripción
Sumario:High-level quantum-chemical computations (G4MP2) are carried out in the study of complexes featuring tetrel bonding between the carbon atom in the carbenoid CBH-obtained by hydride removal in the C-H bond of the known closo-monocarbadodecaborate anion CBH (-) and acting as Lewis acid (LA)-and Lewis bases (LB) of different type; the electron donor groups in the tetrel bond feature carbon, nitrogen, oxygen, fluorine, silicon, phosphorus, sulfur, and chlorine atomic centres in neutral molecules as well as anions H, OH, and F. The empty radial 2pr vacant orbital on the carbon centre in CBH, which corresponds to the LUMO, acts as a Lewis acid or electron attractor, as shown by the molecular electrostatic potential (MEP) and electron localization function (ELF). The thermochemistry and topological analysis of the complexes {CBH:LB} are comprehensively analysed and classified according to shared or closed-shell interactions. ELF analysis shows that the tetrel C…X bond ranges from very polarised bonds, as in H11B11C:F to very weak interactions as in HBC…FH and HBC…O=C=O.