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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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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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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: Overview01:23

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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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Complexometric Titration: Ligands00:43

Complexometric Titration: Ligands

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Different monodentate and polydentate ligands are used as complexing agents in complexometric titration reactions. The formation of complexes by mono- and bidentate ligands involves two or more intermediate steps, limiting their use as complexing agents. In comparison, polydentate ligands can form complexes with metal ions in a single-step process, facilitating sharper end points. This means polydentate ligands, such as amino carboxylic acid derivatives, are most commonly employed in...
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EDTA: Chemistry and Properties01:22

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Polydentate ligands are most widely used in complexometric titrations because they form more stable complexes with the metal ions than mono- or bidentate ligands due to the chelate effect. Examples of polydentate ligands are ethylenediaminetetraacetic acid (EDTA), crown ethers, and cryptands. The most important feature of optimal polydentate ligands is the ability to form 1:1 complexes in a single-step process. Amino carboxylic acid derivatives are frequently used as complexing agents. EDTA is...
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Thermochemical Studies of NiII and ZnII Ternary Complexes Using Ion Mobility-Mass Spectrometry
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Dinitrogen complexation and reduction at low-valent calcium.

B Rösch1, T X Gentner1, J Langer1

  • 1Inorganic Chemistry, University Erlangen-Nürnberg, 91058 Erlangen, Germany.

Science (New York, N.Y.)
|March 12, 2021
PubMed
Summary
This summary is machine-generated.

Researchers explored low-valent calcium(I) complexes under a dinitrogen (N2) atmosphere. They isolated a novel complex, LCa(N2)CaL, which serves as a precursor for the desired calcium(I) compound.

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Area of Science:

  • Inorganic Chemistry
  • Organometallic Chemistry
  • Materials Science

Background:

  • Low-valent main group metal complexes are of significant interest for their unique reactivity.
  • Dinitrogen (N2) activation by metal complexes is a key challenge in chemistry, with implications for nitrogen fixation.
  • Bulky ligands are often employed to stabilize reactive low-valent metal centers.

Purpose of the Study:

  • To synthesize and characterize low-valent calcium(I) complexes.
  • To investigate the reactivity of dinitrogen (N2) coordinated to calcium.
  • To explore the potential of these complexes as synthons for other low-valent calcium species.

Main Methods:

  • Attempted synthesis of low-valent calcium(I) complexes (LCa-CaL) under dinitrogen (N2).
  • Crystallographic characterization of the isolated dinitrogen complex.
  • Investigation of the reactivity of the coordinated dinitrogen anion (N2^2-).

Main Results:

  • Isolation and crystallographic characterization of LCa(N2)CaL.
  • The dinitrogen (N2^2-) anion demonstrated potent two-electron donor capabilities.
  • LCa(N2)CaL was identified as a synthon for the target low-valent calcium(I) complex, LCa-CaL.
  • Protonation of the N2^2- anion led to diazene (N2H2), which disproportionated.

Conclusions:

  • LCa(N2)CaL is a stable complex that serves as a valuable synthon for low-valent calcium(I) chemistry.
  • The coordinated dinitrogen anion exhibits versatile reactivity, acting as a strong electron donor and undergoing protonation.
  • The study provides insights into the role of calcium d orbitals in dinitrogen activation.