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Related Experiment Videos

Ligand macrocycle structural effects on copper-dioxygen reactivity.

B M Lam1, J A Halfen, V G Young

  • 1Department of Chemistry and Center for Metals in Biocatalysis, University of Minnesota, 207 Pleasant Street SE, Minneapolis, Minnesota 55455, USA.

Inorganic Chemistry
|February 24, 2001
PubMed
Summary

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The size of substituents on tridentate macrocyclic ligands influences copper complex stability. Larger substituents favor peroxo complexes, while smaller ones yield bis(mu-oxo) species, impacting oxygen reactivity.

Area of Science:

  • Coordination Chemistry
  • Bioinorganic Chemistry
  • Organometallic Chemistry

Background:

  • Copper complexes with macrocyclic ligands are crucial in bioinorganic chemistry, mimicking enzyme active sites.
  • Understanding the reactivity of copper-oxygen species is vital for catalysis and biological processes.
  • The influence of ligand structure on the stability of peroxo and bis(mu-oxo) dicopper complexes is not fully understood.

Purpose of the Study:

  • To investigate how the steric and electronic properties of tridentate macrocyclic ligands affect the stability of isomeric mu-eta 2:eta 2-peroxo- and bis(mu-oxo)dicopper complexes.
  • To elucidate the factors controlling the oxygenation pathways of Cu(I) complexes with varying macrocyclic ligands.
  • To correlate ligand structure with the observed reactivity and stability of oxygenated copper species.

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Main Methods:

  • Synthesis and characterization of Cu(I) complexes supported by 10- and 12-membered triazamacrocycles (R3TACD and iPr3TACDD).
  • Oxygenation reactions at low temperatures (-80 °C) followed by UV-vis and resonance Raman spectroscopy.
  • X-ray crystallography for structural determination of precursors and oxygenated products.
  • Kinetic studies of oxygenated complex decomposition.
  • Computational modeling using integrated molecular orbital molecular mechanics (IMOMM) methods.

Main Results:

  • Oxygenation of Cu(I) complexes with smaller 10-membered R3TACD ligands (R=Me, Bn) yielded exclusively bis(mu-oxo) dicopper species.
  • In contrast, oxygenation of the Cu(I) complex with the 12-membered iPr3TACDD ligand cleanly produced a mu-eta 2:eta 2-peroxo dicopper complex, with no bis(mu-oxo) formation.
  • Decomposition of oxygenated species primarily involved intramolecular attack at the alpha C-H bonds of ligand substituents, leading to hydroxo and carbonato complexes.
  • Ligand substituent size and macrocycle ring size were identified as key factors governing the relative stability of peroxo and bis(mu-oxo) isomers.

Conclusions:

  • The steric bulk of substituents on the macrocyclic ligand plays a critical role in directing the O2 reaction pathway and stabilizing specific copper-oxygen species.
  • Larger substituents, as in the iPr3TACDD system, favor the formation and stability of the peroxo isomer.
  • Smaller substituents and macrocycle size influence the equilibrium towards the bis(mu-oxo) form, demonstrating a tunable reactivity based on ligand design.