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Related Concept Videos

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,...
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...
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.
Structural Isomerism02:34

Structural Isomerism

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 be...
Ionic Crystal Structures02:42

Ionic Crystal Structures

Ionic crystals consist of two or more different kinds of ions that usually have different sizes. The packing of these ions into a crystal structure is more complex than the packing of metal atoms that are the same size.
Most monatomic ions behave as charged spheres, and their attraction for ions of opposite charge is the same in every direction. Consequently, stable structures for ionic compounds result (1) when ions of one charge are surrounded by as many ions as possible of the opposite...
Stereoisomerism02:52

Stereoisomerism

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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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

Published on: April 10, 2015

Closed-shell and open-shell square-planar iridium nitrido complexes.

Markus G Scheibel1, Bjorn Askevold, Frank W Heinemann

  • 1Institut für Anorganische Chemie, Georg-August-Universität Göttingen, Tammanstraße 4, 37077 Göttingen, Germany.

Nature Chemistry
|June 22, 2012
PubMed
Summary

This study reports novel iridium nitrido complexes, including an open-shell form exhibiting significant nitridyl radical character. This finding advances understanding of nitrogen atom coupling in catalysis and redox non-innocence.

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09:45

Accessing Valuable Ligand Supports for Transition Metals: A Modified, Intermediate Scale Preparation of 1,2,3,4,5-Pentamethylcyclopentadiene

Published on: March 20, 2017

Area of Science:

  • Organometallic Chemistry
  • Catalysis
  • Inorganic Chemistry

Background:

  • Nitrogen atom coupling is crucial for catalytic processes like the Haber-Bosch reaction.
  • The reactivity of nitrido ligands in metal complexes is often linked to M-N bonding.
  • Evidence for nitrogen-centered radical character in nitrido ligands has been suggested but not definitively proven.

Purpose of the Study:

  • To synthesize and characterize novel closed-shell and open-shell iridium nitrido complexes.
  • To investigate the electronic structure and radical character of these complexes.
  • To elucidate the role of nitrido ligand redox non-innocence in coupling reactions.

Main Methods:

  • Synthesis of square-planar iridium nitrido complexes, [IrN(L(t-Bu))](+) and [IrN(L(t-Bu))].
  • Spectroscopic characterization techniques.
  • Quantum chemical calculations.

Main Results:

  • Successful synthesis of novel closed-shell and open-shell iridium nitrido complexes.
  • Spectroscopic and computational data indicate substantial nitridyl {Ir=N(•)} radical character in [IrN(L(t-Bu))].
  • The observed binuclear coupling to form Ir(I)-N(2) complexes is explained by the nitrido ligand's redox non-innocence.

Conclusions:

  • The study provides the first unequivocal spectroscopic characterization of a nitridyl radical complex.
  • Nitrido ligand redox non-innocence plays a key role in the coupling reactivity of these iridium complexes.
  • These findings offer new insights into the mechanisms of nitrogen-involved catalytic reactions.