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Related Concept Videos

Ladder Diagrams: Complexation Equilibria01:07

Ladder Diagrams: Complexation Equilibria

Ladder diagrams are useful for evaluating equilibria involving metal-ligand complexes. The vertical scale of the ladder diagram represents the concentration of unreacted or free ligand, pL. The horizontal lines on the scale depict the log of stepwise formation constants for metal-ligand complexes and indicate the dominant species in all the regions.
The formation constant, K1, for the formation of Cd(NH3)2+ complex from cadmium and ammonia is 3.55 × 102. Log K1 (i.e. pNH3) is 2.55, and...
Coordination Number and Geometry02:57

Coordination Number and Geometry

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.
Metal-Ligand Bonds02:51

Metal-Ligand Bonds

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...
Valence Bond Theory02:42

Valence Bond Theory

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

Crystal Field Theory - Tetrahedral and Square Planar Complexes

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,...
Crystal Field Theory - Octahedral Complexes02:58

Crystal Field Theory - Octahedral Complexes

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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Preparation of SNS Cobalt(II) Pincer Model Complexes of Liver Alcohol Dehydrogenase
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Interconversion between ladder-type octanuclear and linear tetranuclear copper(I) complexes supported by

Yukie Takemura1, Takayuki Nakajima, Tomoaki Tanase

  • 1Department of Chemistry, Faculty of Science, Nara Women's University, Kitauoya-nishi-machi, Nara, 630-8506, Japan.

Dalton Transactions (Cambridge, England : 2003)
|November 19, 2009
PubMed
Summary

This study details the synthesis and structural transformation of octanuclear copper(I) ladder complexes into tetranuclear copper(I) chain complexes using a tetraphosphine ligand. These complexes exhibit interconversion between ladder and chain structures, offering potential as building blocks for larger copper clusters.

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[(DPEPhos)(bcp)Cu]PF6: A General and Broadly Applicable Copper-Based Photoredox Catalyst
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Ion Mobility-Mass Spectrometry Techniques for Determining the Structure and Mechanisms of Metal Ion Recognition and Redox Activity of Metal Binding Oligopeptides
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Ion Mobility-Mass Spectrometry Techniques for Determining the Structure and Mechanisms of Metal Ion Recognition and Redox Activity of Metal Binding Oligopeptides
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Ion Mobility-Mass Spectrometry Techniques for Determining the Structure and Mechanisms of Metal Ion Recognition and Redox Activity of Metal Binding Oligopeptides

Published on: September 7, 2019

Area of Science:

  • Coordination Chemistry
  • Organometallic Chemistry
  • Materials Science

Background:

  • Copper(I) halide complexes are versatile in catalysis and materials science.
  • Tetraphosphine ligands offer unique coordination modes for metal clusters.
  • Understanding cluster assembly and disassembly is crucial for designing novel materials.

Purpose of the Study:

  • To synthesize and characterize novel octanuclear and tetranuclear copper(I) complexes.
  • To investigate the structural interconversion between ladder and chain copper complexes.
  • To explore the potential of these complexes as synthons for extended copper halide clusters.

Main Methods:

  • Reaction of meso-bis[(diphenylphosphinomethyl)phenylphosphino]methane (dpmppm) with copper(I) halides (CuX).
  • Structural characterization using X-ray crystallography.
  • Investigating complex transformations under varying solvent and reagent conditions.

Main Results:

  • Synthesis of octanuclear copper(I) ladder complexes [Cu(8)(mu-X)(8)(mu-dpmppm)(2)].
  • Formation of tetranuclear copper(I) chain complexes [Cu(4)X(mu-X)(3)(mu-dpmppm)(2)(L)] (L = solvent or isocyanide).
  • Demonstration of reversible interconversion between Cu(8) ladder and Cu(4) chain structures.

Conclusions:

  • The dpmppm ligand facilitates the formation of both octanuclear ladder and tetranuclear chain copper(I) complexes.
  • The interconversion between these structures highlights their dynamic nature and potential as building blocks.
  • These findings open avenues for the rational design of extended copper halide cluster architectures.