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Formation of Complex Ions03:45

Formation of Complex Ions

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A type of Lewis acid-base chemistry involves the formation of a complex ion (or a coordination complex) comprising a central atom, typically a transition metal cation, surrounded by ions or molecules called ligands. These ligands can be neutral molecules like H2O or NH3, or ions such as CN− or OH−. Often, the ligands act as Lewis bases, donating a pair of electrons to the central atom. These types of Lewis acid-base reactions are examples of a broad subdiscipline called coordination...
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Lewis Acids and Bases02:33

Lewis Acids and Bases

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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...
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Ionic Bonding and Electron Transfer02:48

Ionic Bonding and Electron Transfer

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Ions are atoms or molecules bearing an electrical charge. A cation (a positive ion) forms when a neutral atom loses one or more electrons from its valence shell, and an anion (a negative ion) forms when a neutral atom gains one or more electrons in its valence shell. Compounds composed of ions are called ionic compounds (or salts), and their constituent ions are held together by ionic bonds: electrostatic forces of attraction between oppositely charged cations and anions. 
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Complexation Equilibria: Overview01:23

Complexation Equilibria: Overview

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Complexation reactions take place when dative or coordinate covalent bonds form between metal ions and ligands. The compounds formed in these reactions are called coordination compounds. The number of bonds formed between the metal ion and the ligands is called its coordination number. Generally, most metal ions in an aqueous solution are solvated by water molecules and thus exist as aqua complexes.
The equilibrium constant of the complexation reaction is represented as the formation constant...
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Common Ion Effect03:24

Common Ion Effect

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Compared with pure water, the solubility of an ionic compound is less in aqueous solutions containing a common ion (one also produced by dissolution of the ionic compound). This is an example of a phenomenon known as the common ion effect, which is a consequence of the law of mass action that may be explained using Le Châtelier’s principle. Consider the dissolution of silver iodide:
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Ionic Strength: Effects on Chemical Equilibria01:19

Ionic Strength: Effects on Chemical Equilibria

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The addition of an inert ionic compound increases the solubility of a sparingly soluble salt. For example, adding potassium nitrate to a saturated solution of calcium sulfate significantly enhances the solubility of calcium sulfate. Le Châtelier's principle cannot predict this shift in the equilibrium. Instead, this could be explained in terms of changes in the effective concentration of the ions in solution in the presence of added inert salt.
In this solution, the primary...
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Inductive Effect Alone Cannot Explain Lewis Adduct Formation and Dissociation at Electrode Interfaces.

Sevan Menachekanian1, Matthew J Voegtle1, Robert E Warburton2

  • 1Department of Chemistry, University of Southern California, Los Angeles, California 90089, United States.

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|March 2, 2023
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Summary
This summary is machine-generated.

Researchers created a Lewis acid-base adduct on an electrode surface. The nitrogen-boron bond cleaves at negative potentials due to ionic effects, crucial for understanding electrocatalysis and electroadsorption.

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Area of Science:

  • Surface Chemistry
  • Electrochemistry
  • Materials Science

Background:

  • Understanding Lewis bonds at electrified interfaces is key for electrocatalysis and electroadsorption.
  • Interfacial complexities often hinder systematic study of these bonds.
  • A model system is needed to probe interfacial Lewis acid-base interactions.

Purpose of the Study:

  • To create and study a main group Lewis acid-base adduct on an electrode surface.
  • To investigate the behavior of this adduct under varying electrode potentials.
  • To elucidate the mechanisms governing Lewis bond cleavage at electrified interfaces.

Main Methods:

  • Formation of a Lewis acid-base adduct using mercaptopyridine (Lewis base) and boron trifluoride (BF3, Lewis acid) on an electrode.
  • Electrochemical measurements to study the adduct's stability and cleavage at different potentials.
  • Investigation of reversibility using Li+BF4- electrolyte.

Main Results:

  • A stable Lewis bond (N-B) was formed between mercaptopyridine and BF3 on an electrode surface.
  • The N-B bond cleaved at potentials negative of approximately -0.3 V vs Ag/AgCl without current.
  • Cleavage was fully reversible when BF3 was supplied from Li+BF4- electrolyte.
  • Both electroinduction and interfacial ionic effects influence the N-B bond.

Conclusions:

  • Interfacial ionic structures and equilibria, not just electroinduction, drive Lewis bond cleavage at negative potentials.
  • This work provides fundamental insights into interfacial Lewis acid-base interactions.
  • The findings are relevant for designing electrocatalytic and electroadsorption systems.