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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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Valence Bond Theory

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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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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 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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Ladder Diagrams: Complexation Equilibria01:07

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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...
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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...
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A Dinitrogen Dicopper(I) Complex via a Mixed-Valence Dicopper Hydride.

Shiyu Zhang1, Hengameh Fallah2, Evan J Gardner1

  • 1Department of Chemistry, Georgetown University, Box 571227, Washington, DC, 20057-1227, USA.

Angewandte Chemie (International Ed. in English)
|July 14, 2016
PubMed
Summary

A new copper complex featuring a bridging dinitrogen ligand was synthesized. This dinuclear copper complex exhibits cooperativity and can activate small molecules, demonstrating potential in catalysis.

Keywords:
copperdinitrogenhydridemixed-valent compoundsreduction

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Area of Science:

  • Inorganic Chemistry
  • Organometallic Chemistry
  • Catalysis

Background:

  • Copper complexes are vital in various catalytic processes.
  • Dinitrogen (N2) activation remains a significant challenge in chemistry.
  • Tris(pyrazolyl)borate (Tp) ligands offer versatile coordination environments for metal centers.

Purpose of the Study:

  • To synthesize and characterize a novel dinuclear copper-dinitrogen complex.
  • To investigate the electronic structure and reactivity of the N2 ligand.
  • To explore the catalytic potential of the copper complex in small molecule activation.

Main Methods:

  • Low-temperature synthesis and isolation of copper complexes.
  • X-ray crystallography for structural determination.
  • Density Functional Theory (DFT) studies for electronic structure analysis.
  • Reactivity studies involving addition of various ligands and substrates.

Main Results:

  • A bridging dinitrogen complex, [(iPr2)TpCu]2(μ-1,2-N2), was successfully synthesized.
  • X-ray crystallography confirmed a slightly activated N2 ligand (N-N bond length: 1.111(6) Å).
  • DFT studies revealed cooperativity in the dinuclear Cu-N2-Cu interaction.
  • The complex readily releases N2 upon addition of MeCN, CNAr(2,6-Me)2, or O2.
  • A key intermediate, [(iPr2)TpCu]2(μ-H), was isolated and showed reduction of unsaturated substrates like CO and phenylacetylene.

Conclusions:

  • The synthesized dinuclear copper complex effectively coordinates and activates dinitrogen.
  • The complex demonstrates cooperative effects between the two copper centers.
  • The intermediate hydride complex shows potential for catalytic reduction of unsaturated molecules.