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Mechanism of Intramolecular C-H Bond Activation in [(LCu)2(m-O)2]2+ (L = 1,4,7-Trialkyl-1,4,7-triazacyclononane): Quantum Mechanical/Molecular Mechanical Modeling

Cramer, C. J.; Kinsinger, C. K.; Pak, Y.
J. Mol. Struct. (Theochem) 2003, 632, 111.

N-Dealkylation in [(LCu)2(m-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(m-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.

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