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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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Coordination compounds and complexes exhibit different colors, geometries, and magnetic behavior, depending on the metal atom/ion and ligands from which they are composed. In an attempt to explain the bonding and structure of coordination complexes, Linus Pauling proposed the valence bond theory, or VBT, using the concepts of hybridization and the overlapping of the atomic orbitals. According to VBT, the central metal atom or ion (Lewis acid) hybridizes to provide empty orbitals of suitable...
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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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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 Number and Geometry

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For transition metal complexes, the coordination number determines the geometry around the central metal ion. Table 1 compares coordination numbers to molecular geometry. The most common structures of the complexes in coordination compounds are octahedral, tetrahedral, and square planar.
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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...
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Preparation, Purification, and Characterization of Lanthanide Complexes for Use as Contrast Agents for Magnetic Resonance Imaging
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Preparation, Purification, and Characterization of Lanthanide Complexes for Use as Contrast Agents for Magnetic Resonance Imaging

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Lanthanide cryptate monometallic coordination complexes.

Christian D Buch1, Dmitri Mitcov1, Stergios Piligkos1

  • 1Department of Chemistry, University of Copenhagen, Universitetsparken 5, DK-2100 Copenhagen, Denmark. piligkos@chem.ku.dk.

Dalton Transactions (Cambridge, England : 2003)
|September 21, 2020
PubMed
Summary
This summary is machine-generated.

Six new lanthanide cryptate complexes were synthesized and characterized. Magnetic studies revealed properties similar to related lanthanide complexes, with specific ions showing out-of-phase susceptibility signals.

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Area of Science:

  • Coordination Chemistry
  • Materials Science
  • Magnetochemistry

Background:

  • Lanthanide coordination complexes are of interest for their unique magnetic and optical properties.
  • Cryptate ligands offer enhanced stability and control over metal ion coordination environments.
  • Previous studies on lanthanide complexes with related ligands (e.g., Ln(trensal)) provide a basis for comparison.

Purpose of the Study:

  • To synthesize and characterize novel neutral lanthanide cryptate coordination complexes.
  • To investigate the structural and magnetic properties of these new complexes.
  • To compare their magnetic behavior with existing lanthanide complexes.

Main Methods:

  • Synthesis via reaction of a specific phenol, amine, and lanthanide triflate salt.
  • Characterization using powder X-ray diffraction and crystal structure analysis.
  • Magnetic property investigation using SQUID magnetometry, including static and dynamic susceptibility measurements.

Main Results:

  • Six isostructural neutral lanthanide cryptate complexes (LnL·4H2O) were successfully synthesized.
  • Crystal structure of the Yb complex revealed a heptacoordinated Ln(iii) center with a distorted octahedral geometry.
  • Dy, Er, and Yb complexes exhibited out-of-phase susceptibility signals, indicative of slow magnetic relaxation.
  • Magnetic relaxation in the Yb complex followed direct and Raman processes at different temperature ranges.

Conclusions:

  • The synthesized lanthanide cryptates are structurally similar to known complexes like Ln(trensal).
  • The magnetic properties are consistent with the presence of Kramers ions (Dy, Er, Yb) and exhibit temperature-dependent relaxation mechanisms.
  • These findings contribute to the understanding of lanthanide magnetism in cryptate environments.