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Inorganic Chemistry, Vol.33, No.8, 1729-1730, 1994
C-H Bond Activation by Cobalt(I) Macrocycles - Rapid H/D Exchange Between Macrocycle and Acetonitrile Solvent
FT-IR and H-1 NMR spectra of CoL+ (L = 5,7,7,12,14,14-hexamethyl-1,4,8,11-tetraazacyclotetradeca-4,11-diene) in CD3CN indicate rapid H/D exchange of the deuterated solvent with the macrocycle amine protons (rate constant (5 +/- 1) X 10(-4) s-1 at (23 +/- 1) degrees-C) and slower exchange with the protons of the imine methyl and the methylene adjacent to the imine carbon atoms (marked with an asterisk in the figure); the process is anomalously rapid for "simple" proton transfer and signals reactivity of the metal center toward C-H activation.
Keywords:CARBON-DIOXIDE ACTIVATION;ELECTROCATALYTIC REDUCTION;AQUEOUS-SOLUTION;COMPLEXES;BINDING;CO2;THERMODYNAMICS;WATER;CATALYSIS;CHEMISTRY