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Quantification of the trans influence in hypervalent iodine complexes.

P K Sajith1, Cherumuttathu H Suresh

  • 1Computational Modeling and Simulation Section, National Institute for Interdisciplinary Science and Technology (CSIR), Trivandrum, India 695 019.

Inorganic Chemistry
|January 3, 2012
PubMed
Summary

This study quantifies the trans influence of ligands in hypervalent iodine complexes. Ligand properties predict bond energies, aiding in designing stable iodine compounds and understanding their reactivity.

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Area of Science:

  • Inorganic Chemistry
  • Computational Chemistry
  • Physical Chemistry

Background:

  • Hypervalent iodine compounds exhibit unique reactivity.
  • Understanding ligand effects is crucial for predicting chemical behavior.

Purpose of the Study:

  • To quantify the trans influence of various ligands in hypervalent iodine(III) and iodine(V) complexes.
  • To establish relationships between trans influence, mutual trans influence, and bond dissociation energies.
  • To develop predictive models for hypervalent iodine compound stability and reactivity.

Main Methods:

  • Quantification of trans influence using I-Cl bond length (d(X)), electron density at the bond critical point (ρ(r)), and molecular electrostatic potential (MESP).
  • Calculation of mutual trans influence using isodesmic reaction energies (E(XY)).
  • Derivation of an empirical equation to predict bond dissociation energies (E(d)).

Main Results:

  • Trans influence in iodine(V) complexes is smaller than in iodine(III) complexes, with similar relative ordering.
  • Mutual trans influence (E(XY)) is accurately predicted by trans-influence parameters (d(X), ρ(r), V(min)).
  • Bond dissociation energies (E(d)) are significantly influenced by both trans and mutual trans influences, with a predictive empirical equation developed.

Conclusions:

  • Quantified trans and mutual trans influence parameters are valuable for assessing hypervalent iodine compound stability.
  • These parameters can guide the design of novel, stable hypervalent iodine complexes.
  • Insights into I-X bond dissociation energies will aid in explaining reactivity and reaction mechanisms of hypervalent iodine complexes.