Mechanism of intramolecular C-H bond activation in [(LCu) 2(μ-O)2]2+ (L = 1,4,7-trialkyl-1,4,7-triazacyclononane): Quantum mechanical/molecular mechanical modeling

Christopher J. Cramer, Christopher R. Kinsinger, Youngshang Pak

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N-dealkylation in [(LCu)2(μ-O)2]2+ (L = 1,4,7-tribenzyl-1,4,7-triazacyclononane) is predicted by quantum-mechanical/molecular-mechanical calculations using density functional theory to take place with the dioxocopper core in a bis(μ-oxo) geometry via a mechanism involving internal hydrogen atom transfer of an equatorially located benzylic H to an oxo oxygen atom. This step is followed by a very-low barrier hydroxyl group rebound to generate an aminal that is hydrolyzed to an aldehyde on aqueous workup. There is some polar character to the H atom-transfer transition state so that it is weakly sensitive to aromatic substitution. At 233 K, tunneling plays a significant role in the kinetics.

Original languageEnglish (US)
Pages (from-to)111-120
Number of pages10
JournalJournal of Molecular Structure: THEOCHEM
Issue number1-3
StatePublished - Aug 1 2003

Bibliographical note

Funding Information:
We thank Don Truhlar and Bill Tolman for helpful discussions on the subjects of tunneling and bis(μ-oxo)dicopper complexes, respectively. This work was supported in part by the National Science Foundation (CHE-0203346).


  • Binuclear copper complex
  • C-H bond activation
  • Hydrogen-atom transfer
  • Kinetic isotope effect
  • Oxygen activation
  • Tunneling


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