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Complexometric Titration: Ligands00:43

Complexometric Titration: Ligands

2.6K
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...
2.6K
EDTA: Chemistry and Properties01:22

EDTA: Chemistry and Properties

3.8K
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...
3.8K
Complexation Equilibria: Factors Influencing Stability of Complexes01:09

Complexation Equilibria: Factors Influencing Stability of Complexes

945
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...
945
Crystal Field Theory - Tetrahedral and Square Planar Complexes02:46

Crystal Field Theory - Tetrahedral and Square Planar Complexes

49.5K
Tetrahedral Complexes
Crystal field theory (CFT) is applicable to molecules in geometries other than octahedral. In octahedral complexes, the lobes of the dx2−y2 and dz2 orbitals point directly at the ligands. For tetrahedral complexes, the d orbitals remain in place, but with only four ligands located between the axes. None of the orbitals points directly at the tetrahedral ligands. However, the dx2−y2 and dz2 orbitals (along the Cartesian axes) overlap with the ligands less than the dxy,...
49.5K
EDTA: Auxiliary Complexing Reagents01:26

EDTA: Auxiliary Complexing Reagents

1.5K
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...
1.5K
Ionic Crystal Structures02:42

Ionic Crystal Structures

20.2K
Ionic crystals consist of two or more different kinds of ions that usually have different sizes. The packing of these ions into a crystal structure is more complex than the packing of metal atoms that are the same size.
Most monatomic ions behave as charged spheres, and their attraction for ions of opposite charge is the same in every direction. Consequently, stable structures for ionic compounds result (1) when ions of one charge are surrounded by as many ions as possible of the opposite...
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Synthesis and Reaction Chemistry of Nanosize Monosodium Titanate
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Synthesis and Reaction Chemistry of Nanosize Monosodium Titanate

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Counteranion-Stabilized Titanium(IV) Isopolyoxocationic Clusters Isolated from Water.

Guanyun Zhang1, Jie Hou1, Mingzhong Li1

  • 1Key Laboratory for Colloid and Interface Chemistry of Ministry of Education, School of Chemistry and Chemical Engineering, Shandong University , Ji'Nan 250199, P. R. China.

Inorganic Chemistry
|April 28, 2016
PubMed
Summary

Researchers synthesized novel titanium(IV) oxo clusters, Ti6 and Ti8, from water. These structures highlight the crucial role of halide counteranions in stabilizing titanium oxide molecular fragments.

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Area of Science:

  • Inorganic Chemistry
  • Materials Science
  • Nanotechnology

Background:

  • Titanium oxide clusters are fundamental building blocks for advanced materials.
  • Synthesis of well-defined titanium(IV) oxo clusters in aqueous media remains challenging.
  • Understanding the role of counterions in stabilizing these clusters is crucial for their application.

Purpose of the Study:

  • To synthesize and characterize novel titanium(IV) oxo clusters using controlled hydrolysis and condensation.
  • To investigate the structural features and stabilization mechanisms of these clusters.
  • To explore the general importance of counteranions in the synthesis of titanium oxide molecular fragments.

Main Methods:

  • Synthesis via controlled hydrolysis and condensation of titanium(IV) halides (TiX4) in aqueous solutions.
  • Structural and compositional analysis using single-crystal and powder X-ray diffraction.
  • Elemental analysis via inductively coupled plasma atomic emission spectrometry and energy-dispersive spectrometry.
  • Computational analysis using density functional theory (DFT) and spectroscopic methods.

Main Results:

  • Successful synthesis of two novel titanium(IV) oxo clusters: [Ti6(Oμ)8(OtH2)20](8+) (Ti6) and [Ti8O12(OH2)24](8+) (Ti8).
  • Ti6 exhibits a structure analogous to Lindqvist polyoxometalates, featuring six-coordinated titanium(IV) atoms bridged by μ2-O atoms.
  • Both Ti6 and Ti8 clusters are stabilized by hydrogen bonding interactions with their halide counteranions.

Conclusions:

  • This study reports the second example of a titanium(IV) isopolyoxocationic cluster isolated from water.
  • The findings demonstrate that halide counteranions play a critical role in the stabilization and synthesis of molecular titanium oxide fragments.
  • The results suggest a general strategy for synthesizing diverse titanium oxide nanostructures by controlling counteranion interactions.