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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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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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Metal ions can be separated from one another by complexation with organic ligands–the chelating agent– to form uncharged chelates. Here, the chelating agent must contain hydrophobic groups and behave as a weak acid, losing a proton to bind with the metal. Since most organic ligands used in this process are insoluble or undergo oxidation in the aqueous phase, the chelating agent is initially added to the organic phase and extracted into the aqueous phase. The metal-ligand complex is...
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Crystal Field Theory
To explain the observed behavior of transition metal complexes (such as colors), a model involving electrostatic interactions between the electrons from the ligands and the electrons in the unhybridized d orbitals of the central metal atom has been developed. This electrostatic model is crystal field theory (CFT). It helps to understand, interpret, and predict the colors, magnetic behavior, and some structures of coordination compounds of transition metals.
CFT focuses on...
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EDTA titrations are usually carried out in highly basic conditions, where the fully deprotonated form of EDTA, Y4−, actively complexes with the free metal ions in the solution. Several metal ions precipitate as hydrous oxide (hydroxides, oxides, or oxyhydroxides) under these conditions, lowering the concentration of free metal ions in the solution. For this reason, auxiliary complexing agents or ligands such as ammonia, tartrate, citrate, or triethanolamine are used in EDTA titrations to...
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Metal-Ligand Bonds

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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.
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In Situ Synthesis of Gold Nanoparticles without Aggregation in the Interlayer Space of Layered Titanate Transparent Films
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Cationic Gold(II) Complexes: Experimental and Theoretical Study.

Jaya Mehara1, Adarsh Koovakattil Surendran1, Teun van Wieringen1

  • 1Department of Spectroscopy and Catalysis, Institute for Molecules and Materials, Radboud University Nijmegen, Heyendaalseweg 135, 6525AJ, Nijmegen (The, Netherlands.

Chemistry (Weinheim an Der Bergstrasse, Germany)
|August 10, 2022
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Summary
This summary is machine-generated.

Researchers explored rare Gold(II) complexes, finding that specific nitrogen-donor ligands stabilize them. These Gold(II) complexes exhibit properties similar to copper(II) complexes.

Keywords:
density functional calculationselectronic spectroscopygoldmass spectrometryvibrational spectroscopy

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Area of Science:

  • Inorganic Chemistry
  • Organometallic Chemistry
  • Computational Chemistry

Background:

  • Gold(II) complexes are exceptionally rare due to their instability, readily oxidizing to Gold(III) or reducing to Gold(I).
  • The catalytic applications of Gold(II) species remain largely unexplored because of their transient nature.

Purpose of the Study:

  • To investigate the thermodynamic stability of gaseous Gold(II) complexes, specifically [AuII(L)(X)]+.
  • To explore the influence of ancillary ligands (L) and halogens (X) on Gold(II) complex stability.
  • To characterize the spectral (IR and visible) and electronic properties of these rare Gold(II) complexes.

Main Methods:

  • Thermodynamic analysis of Gold(II) complex formation from Gold(III) precursors.
  • Spectroscopic characterization in the infrared (IR) and visible regions.
  • Quantum chemical calculations to correlate electronic structure with observed properties.

Main Results:

  • Bidentate and tridentate nitrogen-donor ligands were identified as optimal for stabilizing gaseous Gold(II) complexes.
  • The electronic structure and spectral properties of the studied Gold(II) complexes closely resemble those of analogous Copper(II) complexes.
  • Gas-phase stability and spectral data were obtained for various [AuII(L)(X)]+ complexes.

Conclusions:

  • Specific ligand design, particularly using polydentate nitrogen donors, can stabilize elusive Gold(II) species in the gas phase.
  • The electronic and spectroscopic similarities suggest potential parallels in reactivity and application between Gold(II) and Copper(II) systems.
  • This study provides foundational insights into the chemistry of Gold(II) complexes, opening avenues for future catalytic research.