Syntheses and Characterization of Two Dioxygen Reactive Dinuclear Macrocyclic Schiff-base Copper(I) Complexes

D Utz, FW Heinemann, F Hampel, David Trevor Richens, S Schindler

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38 Citations (Scopus)

Abstract

The dinuclear copper(I) complex [Cu2L1(CH3CN)(2)](ClO4)(2) (1, L-1 = 3,6,9,17,20,23-hexaazatricyclo[23.3.1.1]triaconta-1(29),2,9,11(30),12(13),14,16,23,25,27-decaene) has been structurally characterized. As previously described, intramolecular ligand hydroxylation (at the aromatic ring) was observed when 1 was reacted with dioxygen. A stopped-flow analysis of the reaction of 1 With dioxygen under different conditions did not allow a "dioxygen intermediate" to be spectroscopically detected. Detailed NMR and electrochemical data on 1 are also presented and evaluated for the first time. No copper(II) complexes of L-1 could be characterized due to hydrolysis of the compounds. In contrast, complex 2-differing from 1 only in an increase in the size of the chelate rings-did not undergo intramolecular hydroxylation when it was oxidized. The crystal structure of 2 is also described.

Original languageEnglish
Pages (from-to)1430-1436
Number of pages7
JournalInorganic Chemistry
Volume42
Issue number5
DOIs
Publication statusPublished - 10 Mar 2003

Keywords

  • C-H BOND
  • INTRAMOLECULAR LIGAND HYDROXYLATION
  • MONOOXYGENASE MODEL SYSTEM
  • RAY CRYSTAL-STRUCTURE
  • OXYGEN INSERTION
  • BINUCLEATING LIGANDS
  • DICOPPER COMPLEXES
  • METAL-COMPLEXES
  • HIGH-PRESSURE
  • TYROSINASE

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