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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,...
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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...
Crystal Field Theory - Octahedral Complexes02:58

Crystal Field Theory - Octahedral Complexes

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...
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.
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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Effect of Lone Pairs of Electrons on Molecule Geometry

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Updated: Jul 5, 2026

Amide Coupling Reaction for the Synthesis of Bispyridine-based Ligands and Their Complexation to Platinum as Dinuclear Anticancer Agents
07:20

Amide Coupling Reaction for the Synthesis of Bispyridine-based Ligands and Their Complexation to Platinum as Dinuclear Anticancer Agents

Published on: May 28, 2014

The trans effect in square-planar platinum(II) complexes--a density functional study.

Zdenek Chval1, Miroslav Sip, Jaroslav V Burda

  • 1Department of Biophysics, Faculty of Health and Social Studies, University of South Bohemia, J. Boreckeho 27, 370 11 Ceske Budejovice, Czech Republic. chval@jcu.cz

Journal of Computational Chemistry
|April 30, 2008
PubMed
Summary

The trans effect in platinum complexes is driven by sigma-donation and pi-back-donation, influencing reaction mechanisms. Ligand properties dictate whether substitution proceeds via dissociative, associative, or interchange pathways.

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Published on: June 24, 2022

Area of Science:

  • Inorganic Chemistry
  • Coordination Chemistry
  • Reaction Mechanisms

Background:

  • Square planar platinum(II) complexes are crucial in coordination chemistry.
  • Understanding substitution reactions is key to predicting complex behavior.
  • The trans effect significantly influences reactivity in these systems.

Purpose of the Study:

  • To elucidate the mechanism of substitution water exchange reactions in square planar trans-Pt[(NH(3))(2)T(H(2)O)](n+) complexes.
  • To explain the trans effect using sigma-donation and pi-back-donation principles.
  • To correlate ligand properties with reaction pathways and kinetics.

Main Methods:

  • Computational study of platinum complexes with various trans-ligands (T).
  • Quantification of sigma-donation and pi-back-donation via electron occupations of Pt 5d orbitals.
  • Analysis of Pt-H(2)O bond lengths and transition state stabilization.

Main Results:

  • Sigma-donation strength correlates linearly with Pt-H(2)O bond length (trans influence).
  • Kinetic trans effect strength is proportional to sigma-donation, except for strong pi-back-donors.
  • Reaction mechanisms (Id, associative, Ia) depend on ligand electronic properties.

Conclusions:

  • The trans effect arises from competition for electron density donation to the Pt(II) center.
  • Strong sigma-donors (e.g., CH(3)(-), H(-)) favor dissociative interchange (Id).
  • Strong pi-back-donors (e.g., C(2)H(4)) promote associative mechanisms.
  • Weak donors lead to associative interchange (Ia) mechanisms.