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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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Color in Coordination Complexes
When atoms or molecules absorb light at the proper frequency, their electrons are excited to higher-energy orbitals. For many main group atoms and molecules, the absorbed photons are in the ultraviolet range of the electromagnetic spectrum, which cannot be detected by the human eye. For coordination compounds, the energy difference between the d orbitals often allows photons in the visible range to be absorbed and emitted, which is seen as colors by the human...
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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.
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Crystal Field Theory - Octahedral Complexes02:58

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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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Crystal Field Theory - Tetrahedral and Square Planar Complexes02:46

Crystal Field Theory - Tetrahedral and Square Planar Complexes

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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 the dxy,...
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Formation of Complex Ions03:45

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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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Preparation of SNS CobaltII Pincer Model Complexes of Liver Alcohol Dehydrogenase
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Conformational polymorphism in a cobalt(II) dithiocarbamate complex.

Jetnipat Songkerdthong1, Phimphaka Harding1, David J Harding1

  • 1Functional Materials and Nanotechnology Center of Excellence, Walailak University, Thasala, Nakhon Si Thammarat 80160, Thailand.

Acta Crystallographica. Section C, Structural Chemistry
|September 5, 2020
PubMed
Summary
This summary is machine-generated.

Two distinct crystal forms of a cobalt complex, [TpPh2Co(S2CNBu2)], were synthesized. These polymorphs exhibit different molecular geometries and intermolecular interactions, influencing their solid-state structures.

Keywords:
cobalt complexconformational polymorphismcrystal structuredithiocarbamaterecrystallization

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Area of Science:

  • Coordination Chemistry
  • Crystallography
  • Solid-State Chemistry

Background:

  • Cobalt complexes with dithiocarbamate and hydroborate ligands are of interest for their diverse coordination geometries.
  • Polymorphism, the ability of a compound to crystallize in multiple forms, can significantly impact material properties.

Purpose of the Study:

  • To synthesize and characterize two distinct conformational polymorphs of a novel cobalt(II) complex.
  • To investigate the structural differences and intermolecular interactions between these polymorphs.

Main Methods:

  • Recrystallization from different solvent systems (dichloromethane-methanol and acetonitrile) to isolate polymorphs.
  • Single-crystal X-ray crystallography at 150 K to determine precise atomic arrangements.
  • Infrared (IR) spectroscopy for vibrational analysis.
  • Hirshfeld surface analysis to quantify intermolecular interactions.

Main Results:

  • Two polymorphs, 1a (orthorhombic, Pbca) and 1b (triclinic, P-1), were obtained.
  • Polymorph 1a features a trans orientation of butyl groups and an intermediate five-coordinate geometry.
  • Polymorph 1b exhibits a cis orientation of butyl groups and a square-pyramidal geometry.
  • Hirshfeld analysis indicated 1a favors C-H...S interactions, while 1b favors C-H...π interactions.

Conclusions:

  • The crystallization conditions dictate the conformational polymorph and resulting coordination geometry of the cobalt complex.
  • Subtle differences in ligand orientation lead to variations in intermolecular interactions and crystal packing.
  • Understanding polymorphism is crucial for controlling the solid-state properties of coordination compounds.