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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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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...
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Complexation Equilibria: Factors Influencing Stability of Complexes01:09

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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...
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Complexation Equilibria: The Chelate Effect01:19

Complexation Equilibria: The Chelate Effect

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In complexation reactions, metal atoms or cations interact with ligands to form donor-acceptor adducts called metal complexes. Ligands that bind through one donor site are monodentate, ligands with two donor sites are bidentate, and those with more than two donor sites are polydentate ligands. For example, ethylene diamine is a bidentate ligand that binds through two nitrogen donor atoms, forming a five-membered ring. EDTA is a polydentate ligand that binds through four oxygen and two nitrogen...
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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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Alkyl Halides02:45

Alkyl Halides

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Structural Properties
Alkyl halides are halogen-substituted alkanes wherein one or more hydrogen atoms of an alkane is replaced by a halogen atom such as fluorine, chlorine, bromine, or iodine. The carbon atom in an alkyl halide is bonded to the halogen atom, which is sp3-hybridized and exhibits a tetrahedral shape.
Unlike alkyl halides, compounds in which a halogen atom is bonded to an sp2 -hybridized carbon atom of a carbon-carbon double bond (C=C) are called vinyl halides. Whereas aryl...
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Bi(III) halometallate ionic liquids: Interactions and speciation.

Rebecca Rowe1, Kevin R J Lovelock2, Patricia A Hunt1

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|July 9, 2021
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Bismuth halometallates form novel ionic liquid solvents. Computational studies reveal prevalent dimeric/trimeric anions and weak cation-anion interactions, validating experimental spectra.

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Area of Science:

  • Materials Science
  • Computational Chemistry
  • Inorganic Chemistry

Background:

  • Bismuth compounds are vital for optical, electronic, and dense liquid applications.
  • Bismuth(III) halometallates are promising ionic liquid solvents, but lack fundamental understanding.
  • Experimental characterization of these novel materials is limited.

Purpose of the Study:

  • To computationally investigate Bismuth(III) halometallates with chloride, bromide, and iodide.
  • To understand the speciation, structure, and interactions within these ionic liquids.
  • To validate computational models against experimental spectroscopic data.

Main Methods:

  • Density Functional Theory (DFT) using B3LYP-D3BJ/aug-cc-pVDZ.
  • Investigation of isolated anions and clusters with 1-ethyl-3-methyl-imidazolium ([C2C1Im]+) cations.
  • Gas-phase and polarizable continuum solvation models were employed.

Main Results:

  • Dimeric or trimeric bismuth halide anions are prevalent, with higher charges (-2, -3) observed.
  • Multiple low-energy conformers and key structural patterns in ion-pair and neutral clusters were identified.
  • Weak cation-anion interactions (Coulombic, dispersion) dominate, favoring anion-π structures; charge transfer is minimal but mutual polarization is significant.

Conclusions:

  • Computational models successfully reproduce key features of experimental X-ray photoelectron, UV-Vis, and Raman spectra.
  • The study provides fundamental insights into the structure and interactions of bismuth-based ionic liquids.
  • Findings facilitate the rational design and application of these novel materials.