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Related Concept Videos

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.
Linkage isomers occur when the coordination compound contains a ligand that can bind to the transition metal center through two different atoms. For example, the CN− ligand can bind through the carbon atom or through the nitrogen atom. Similarly, SCN− can...
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Structure of Amines01:19

Structure of Amines

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The hybridized nitrogen atom in amines possesses a lone pair of electrons and is bound to three substituents with a bond angle of around 108°, which is less than the tetrahedral angle of 109.5°. However, the C–N–H bond angle is slightly larger at 112°, with a carbon–nitrogen bond length of 147 pm. This carbon–nitrogen bond length of of amines is longer than the carbon–oxygen bond of alcohols (143 pm) but shorter than alkanes’ carbon–carbon bond (154 pm). These aspects are...
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Stereoisomerism02:52

Stereoisomerism

14.5K
Isomerism in Complexes
Isomers are different chemical species that have the same chemical formula.
Transition metal complexes often exist as geometric isomers, in which the same atoms are connected through the same types of bonds but with differences in their orientation in space. Coordination complexes with two different ligands in the cis and trans positions from a ligand of interest form isomers. For example, the octahedral [Co(NH3)4Cl2]+ ion has two isomers (Figure 1) In the cis...
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Valence Bond Theory02:42

Valence Bond Theory

11.6K
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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Crystal Field Theory - Octahedral Complexes02:58

Crystal Field Theory - Octahedral Complexes

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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...
31.6K
Crystal Field Theory - Tetrahedral and Square Planar Complexes02:46

Crystal Field Theory - Tetrahedral and Square Planar Complexes

49.5K
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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Amide Coupling Reaction for the Synthesis of Bispyridine-based Ligands and Their Complexation to Platinum as Dinuclear Anticancer Agents
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Interconversion between [Fe4S4] and [Fe2S2] Clusters Bearing Amide Ligands.

Kazuki Tanifuji1, Shunichi Tajima1, Yasuhiro Ohki1

  • 1Department of Chemistry, Graduate School of Science and Research Center for Materials Science, Nagoya University , Furo-cho, Chikusa-ku, Nagoya 464-8602, Japan.

Inorganic Chemistry
|April 12, 2016
PubMed
Summary

Synthetic iron-sulfur clusters ([Fe4S4]) can reversibly convert to smaller iron-sulfur clusters ([Fe2S2]) in the presence of pyridines, mimicking biological processes.

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Area of Science:

  • Bioinorganic Chemistry
  • Coordination Chemistry
  • Biochemistry

Background:

  • Iron-sulfur clusters are crucial in biological systems, particularly in oxygen sensing.
  • Structural interconversion between [Fe4S4] and [Fe2S2] clusters is a proposed mechanism in O2-sensing proteins.
  • Synthetic models are needed to understand these cluster transformations.

Purpose of the Study:

  • To investigate the unprecedented structural conversion of synthetic [Fe4S4] clusters to [Fe2S2] clusters.
  • To explore the reversibility and thermodynamics of this cluster interconversion.
  • To provide insights into the mechanisms of O2-sensing proteins.

Main Methods:

  • Synthesis of an all-ferric [Fe4S4](4+) cluster, Fe4S4{N(SiMe3)2}4.
  • Treatment of the [Fe4S4] cluster with pyridines to form [Fe2S2] clusters.
  • Determination of thermodynamic parameters for the equilibrium between cluster forms.
  • Chemical reduction and oxidation experiments to induce and reverse cluster assembly.

Main Results:

  • An all-ferric [Fe4S4] cluster was found to split into [Fe2S2] clusters in the presence of pyridines.
  • The structural conversion between [Fe4S4] and [Fe2S2] clusters was demonstrated to be reversible.
  • Thermodynamic parameters for the equilibrium reactions were determined.
  • Reduction of [Fe2S2] clusters led to [Fe4S4] assembly, which could be re-split by oxidation.

Conclusions:

  • Synthetic [Fe4S4] clusters can be converted to [Fe2S2] clusters, supporting their role in O2-sensing proteins.
  • The reversible nature of this transformation was established, with thermodynamic data provided.
  • This study offers a valuable synthetic model for understanding iron-sulfur cluster dynamics in biological systems.