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Valence Bond Theory02:42

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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Coordination Number and Geometry02:57

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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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Metal-Ligand Bonds02:51

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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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Crystal Field Theory - Tetrahedral and Square Planar Complexes02:46

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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...
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Coordination Compounds and Nomenclature02:54

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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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EDTA: Chemistry and Properties01:22

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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...
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Updated: May 4, 2026

The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes
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The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes

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A tetracoordinated phosphasalen nickel(III) complex.

Thi-Phuong-Anh Cao1, Grégory Nocton, Louis Ricard

  • 1Laboratoire Hétéroéléments et Coordination, CNRS, École Polytechnique, Route de Saclay, 91128 Palaiseau (France) http://www.dcph.polytechnique.fr.

Angewandte Chemie (International Ed. in English)
|December 31, 2013
PubMed
Summary
This summary is machine-generated.

A novel nickel complex with a phosphasalen ligand readily oxidizes to a stable Ni(III) state. This high-valent nickel complex, unlike its salen counterparts, demonstrates remarkable stability due to the ligand

Keywords:
high-valent metalsiminophosphoranesnickelone-electron oxidationphosphasalens

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Thermochemical Studies of NiII and ZnII Ternary Complexes Using Ion Mobility-Mass Spectrometry
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Thermochemical Studies of NiII and ZnII Ternary Complexes Using Ion Mobility-Mass Spectrometry
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Area of Science:

  • Coordination Chemistry
  • Organometallic Chemistry
  • Inorganic Chemistry

Background:

  • Salen ligands are well-known for their ability to stabilize metal complexes.
  • Oxidation of Ni(II) complexes to higher oxidation states is often challenging and requires specific conditions.
  • The electronic properties of ligands significantly influence the stability and reactivity of metal centers.

Purpose of the Study:

  • To investigate the oxidation of a Ni(II) complex featuring a tetradentate phosphasalen ligand.
  • To characterize the resulting oxidized species and determine the site of oxidation.
  • To explore the influence of the phosphasalen ligand on the stability of high-valent nickel species.

Main Methods:

  • Synthesis of a Ni(II) complex with a phosphasalen ligand.
  • Oxidation using a silver salt.
  • Characterization via NMR, EPR, UV/Vis spectroscopy, X-ray diffraction, and magnetic measurements.
  • Density Functional Theory (DFT) calculations.

Main Results:

  • The Ni(II) complex was easily oxidized to a Ni(III) species upon addition of a silver salt.
  • Spectroscopic, crystallographic, and magnetic data confirmed the presence of a high-valent Ni(III) center.
  • Spin density was found to be concentrated on the nickel center, indicating metal-centered oxidation.
  • This Ni(III) complex exhibited unusual stability compared to related salen complexes.

Conclusions:

  • The phosphasalen ligand's strong electron-donating properties facilitate the stabilization of a tetracoordinated Ni(III) complex.
  • This study presents a rare example of a stable, high-valent nickel complex with a phenoxide ligand.
  • The findings expand the understanding of redox chemistry in nickel complexes and ligand design.