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Metal-Ligand Bonds02:51

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.
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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Complexometric Titration: Ligands00:43

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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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Coordination Compounds and Nomenclature02:54

Coordination Compounds and Nomenclature

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In most main group element compounds, the valence electrons of the isolated atoms combine to form chemical bonds that satisfy the octet rule. For instance, the four valence electrons of carbon overlap with electrons from four hydrogen atoms to form CH4. The one valence electron leaves sodium and adds to the seven valence electrons of chlorine to form the ionic formula unit NaCl (Figure 1a). Transition metals do not normally bond in this fashion. They primarily form coordinate covalent bonds, a...
28.6K
Structural Isomerism02:34

Structural Isomerism

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Isomerism in Complexes
Isomers are different chemical species that have the same chemical formula. Structural isomerism of coordination compounds can be divided into two subcategories, the linkage isomers and coordination-sphere isomers.
Linkage isomers occur when the coordination compound contains a ligand that can bind to the transition metal center through two different atoms. For example, the CN− ligand can bind through the carbon atom or through the nitrogen atom. Similarly,...
22.7K
Complexation Equilibria: The Chelate Effect01:19

Complexation Equilibria: The Chelate Effect

1.7K
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...
1.7K
Extraction: Advanced Methods00:56

Extraction: Advanced Methods

1.3K
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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Silver coordination polymers with tri- and hexacyanoethyl-functionalized macrocyclic ligands.

Zhen Ma1, Huaduan Shi, Xiuqiang Deng

  • 1Guangxi Key Laboratory of Petrochemical Resource Processing and Process Intensification Technology, School of Chemistry and Chemical Engineering, Guangxi University, Nanning 530004, P. R. China. mzmz2009@sohu.com.

Dalton Transactions (Cambridge, England : 2003)
|November 27, 2014
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Summary

New macrocyclic compounds functionalized with cyanoethyl groups were synthesized and complexed with silver. These silver complexes form intricate coordination polymers with diverse structural and electronic properties, offering potential for advanced materials applications.

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Synthesis of a Thiol Building Block for the Crystallization of a Semiconducting Gyroidal Metal-sulfur Framework
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Area of Science:

  • Coordination Chemistry
  • Materials Science
  • Supramolecular Chemistry

Background:

  • Macrocyclic compounds offer versatile platforms for constructing complex molecular architectures.
  • Functionalization of macrocycles with specific groups can tailor their coordination behavior and material properties.
  • Silver coordination complexes are of interest due to their diverse applications in catalysis and materials science.

Purpose of the Study:

  • To synthesize novel tri- and hexa-cyanoethyl functionalized macrocyclic compounds.
  • To investigate the coordination chemistry of these macrocycles with silver nitrate.
  • To characterize the resulting silver complexes and coordination polymers, including their structural, thermal, and electrochemical properties.

Main Methods:

  • Synthesis of macrocycles via [1+1] or [2+2] cyclocondensation reactions.
  • Hydrogenation and cyano-functionalization of macrocyclic precursors.
  • Formation of silver complexes and coordination polymers.
  • Characterization using elemental analysis, NMR, IR, ESI-MS, and single-crystal X-ray diffraction.

Main Results:

  • Successful synthesis of 17- and 42-membered tri- and hexa-cyanoethyl functionalized macrocycles.
  • Formation of a discrete silver complex ([AgL(1)](NO3)) and two coordination polymers ([Ag2(NO3)2L(1)]n and {[Ag2](NO3)2}n).
  • X-ray diffraction revealed diverse coordination environments for silver ions (pentacoordinated, octahedral, square-pyramidal, square-planar).
  • Ligands exhibited varying denticity (pentadentate and octadentate).
  • Cyanoethyl groups played a crucial role in forming 2D frameworks with hexametallic macrocyclic and cyclic sets.
  • Thermal and electrochemical properties of the silver complexes were investigated.

Conclusions:

  • The study successfully synthesized novel functionalized macrocycles and their silver complexes.
  • The diverse coordination modes and structural motifs highlight the versatility of these macrocycles in coordination chemistry.
  • The formation of 2D coordination polymers with intricate cyclic structures demonstrates potential for designing advanced functional materials.