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Related Concept Videos

Lewis Acids and Bases02:33

Lewis Acids and Bases

In 1923, G. N. Lewis proposed a generalized definition of acid-base behavior in which acids and bases are identified by their ability to accept or to donate a pair of electrons and form a coordinate covalent bond.
A coordinate covalent bond (or dative bond) occurs when one of the atoms in the bond provides both bonding electrons. For example, a coordinate covalent bond occurs when a water molecule combines with a hydrogen ion to form a hydronium ion. A coordinate covalent bond also results when...
Lewis Acids and Bases02:16

Lewis Acids and Bases

This lesson delves into Lewis acids and bases in the context of the octet rule for electron-deficient compounds. Here, the concept is discussed, emphasizing the group 13 elements like boron or aluminium. Since group 13 elements possess three valence electrons, they form trivalent compounds with a sextet of electrons and a vacant orbital for the central atom. Consequently, these electron-deficient compounds accept electrons from other species to complete their octet in a chemical reaction. They...
Complexation Equilibria: Factors Influencing Stability of Complexes01:09

Complexation Equilibria: Factors Influencing Stability of Complexes

In complexation reactions, metal cations are the electron pair acceptors, and the ligands are the electron pair donors. The stability of the metal complexes depends primarily on the complexing ability of the central metal ion and the nature of the ligands. Generally, the complexing ability of the metal ion depends on the size and charge of the ion. As the metal ion size increases, the stability of the metal complexes decreases, provided that the valency of the metal ion and the ligands remain...
Metal-Ligand Bonds02:51

Metal-Ligand Bonds

The hemoglobin in the blood, the chlorophyll in green plants, vitamin B-12, and the catalyst used in the manufacture of polyethylene all contain coordination compounds. Ions of the metals, especially the transition metals, are likely to form complexes.
In these complexes, transition metals form coordinate covalent bonds, a kind of Lewis acid-base interaction in which both of the electrons in the bond are contributed by a donor (Lewis base) to an electron acceptor (Lewis acid). The Lewis acid in...
Lewis Symbols and the Octet Rule02:36

Lewis Symbols and the Octet Rule

Chemical bonds are complex interactions between two or more atoms or ions, which reduce the potential energy of the molecule. Gilbert N. Lewis developed a model called the Lewis model that simplified the depiction of chemical bond formation and provided straightforward explanations for the chemical bonds seen in most common compounds.
Ligand Binding and Linkage00:49

Ligand Binding and Linkage

Allosteric proteins have more than one ligand binding site; the binding of a ligand to any of these sites influences the binding of ligands to the other sites. When a protein is allosteric, its binding sites are called coupled or linked.  In the case of enzymes, the site that binds to the substrate is known as the active site and the other site is known as the regulatory site. When a ligand binds to the regulatory site, this leads to conformational changes in the protein that can influence the...

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Characterizing Lewis Pairs Using Titration Coupled with In Situ Infrared Spectroscopy
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Published on: February 20, 2020

Labile ligands on some Lewis super acids: a computational study.

Paola Nava1, Yannick Carissan, Stéphane Humbel

  • 1Aix-Marseille Université, Institut des Sciences Moléculaires de Marseille ISM2-UMR-CNRS-6263, Campus St. Jérôme, Marseille cedex 20, France. paola.nava@univ-cezanne.fr

Physical Chemistry Chemical Physics : PCCP
|August 13, 2009
PubMed
Summary

Lewis super-acids like tin(IV) triflate catalyze reactions by coordinating solvent molecules, not just triflate ligands. This study reveals solvent molecules directly bind to metal centers, impacting catalytic activity.

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Area of Science:

  • Organometallic Chemistry
  • Catalysis
  • Computational Chemistry

Background:

  • Lewis super-acids, such as tin(IV) triflate (Sn(OTf)4) and indium(III) triflate (In(OTf)3), are effective catalysts for cycloisomerization reactions.
  • Understanding the coordination environment around these metal centers is crucial for optimizing catalytic performance.

Purpose of the Study:

  • To investigate the coordination behavior of ligands and solvent molecules around Lewis super-acid catalysts using computational methods.
  • To determine the relative interaction strengths between metal centers and various potential coordinating species.

Main Methods:

  • Density functional theory (DFT) calculations were employed to model the interactions.
  • The study focused on a tin-based Lewis super-acid, Sn(OTf)4, as a representative example.
  • Interactions with common reaction medium molecules like nitromethane, esters, diesters, and dimethyl sulfoxide were analyzed.

Main Results:

  • A clear hierarchy of interaction strengths between the metal center and different molecules was established.
  • Dimethyl sulfoxide (DMSO) was found to be capable of displacing triflate ligands from the tin center.
  • This indicates that solvent molecules actively coordinate to the metal center.

Conclusions:

  • Solvent molecules play a direct role in coordinating to Lewis super-acid metal centers.
  • Triflate ligands, despite being anions, may exist as non-coordinating species in solution under certain conditions.
  • These findings have implications for understanding and designing more efficient catalytic systems.