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Stereoisomerism02:52

Stereoisomerism

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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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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 the dxy,...
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Structural Isomerism02:34

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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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Radical Reactivity: Steric Effects01:10

Radical Reactivity: Steric Effects

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The presence of electron-donating, electron-withdrawing, or conjugating groups adjacent to a radical center, imparts electronic stabilization to the radicals. Examples of such electronically-stabilized radicals are triphenylmethyl, tetramethylpiperidine‐N‐oxide, and 2,2‐diphenyl‐1‐picrylhydrazyl. These radicals are remarkably stable and are known as persistent radicals. Some of the persistent radicals can even be isolated and purified.
Along with electronic...
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Resonance02:52

Resonance

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The Lewis structure of a nitrite anion (NO2−) may actually be drawn in two different ways, distinguished by the locations of the N-O and N=O bonds. 
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Updated: Sep 6, 2025

The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes
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Pushing steric limits in osmium(IV) tetraaryl complexes.

Joseph M Parr1, Clarissa Olivar1, Thomas Saal1

  • 1Department of Chemistry, University of Southern California, Los Angeles, California 90089, USA. inkpen@usc.edu.

Dalton Transactions (Cambridge, England : 2003)
|June 30, 2022
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Summary

New synthetic routes improve yields for osmium(IV) tetraaryl complexes, making these organometallic compounds more accessible. This research clarifies the impact of ligand steric bulk on synthesis and explores their tunable electronic properties for materials science applications.

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Area of Science:

  • Organometallic Chemistry
  • Materials Science
  • Synthetic Chemistry

Background:

  • Osmium(IV) tetraaryl complexes are valuable in materials science but challenging to synthesize.
  • Traditional methods using osmium tetroxide (OsO4) result in low yields (≤34%) and involve hazardous reagents.

Purpose of the Study:

  • To develop improved synthetic methods for osmium(IV) tetraaryl complexes with higher yields.
  • To investigate the relationship between ligand steric bulk and complex formation.
  • To explore the electronic properties and potential applications of these complexes.

Main Methods:

  • Synthesis of M(aryl)4 compounds (M = Os, Ru) using novel (Oct4N)2[MX6] precursors.
  • Preparation of Os(mesityl)4 (Os3) for the first time.
  • Structural analysis via single-crystal X-ray diffraction.
  • Characterization using variable-temperature 1H NMR and cyclic voltammetry.
  • Quantification of ligand steric properties using cone angle and percentage buried volume.

Main Results:

  • Yields for known M(aryl)4 complexes increased to ≤73% using new precursors.
  • Os(mesityl)4 was synthesized, demonstrating the method's capability for bulky ligands.
  • A clear correlation between ligand steric bulk and Os(aryl)4 yield was established.
  • Structural data revealed that aryl substituent accommodation influences reaction yields.
  • Redox potentials of Os(aryl)4 complexes were tunable by varying aryl substituents, with Os3 showing a new redox event.

Conclusions:

  • The new synthetic approach offers a less hazardous and more efficient route to osmium(IV) tetraaryl complexes.
  • Ligand steric bulk is a critical factor controlling the yield of these complexes.
  • The tunable electronic properties and structural diversity advance their potential in molecular materials science.