title: The chemistry of nitrogen coordinated tertiary carboxamides: a spectroscopic study on bis(picolyl)amidecopper(II) complexes.
abstract: Metal coordination of the electrically neutral nitrogen atom of a tertiary carboxamide reduces the barrier to C-N-bond rotation and activates the amide towards methanolysis. X-Ray crystallographic studies indicate that this reactivity is correlated to a lifting of the amide resonance structure and concurrent pyramidalization at nitrogen. However, mechanistic data in solution have not been obtained. It became evident that structural mobility is characteristic of the complexes and the crystallographic data do not fully account for relevant reactive species. In this report we summarize IR, UV-vis, and EPR spectra of amide nitrogen coordinated bis(picolyl)amide complexes with copper(II) triflate and copper(II) chloride. A comparison between spectra sampled in the aprotic solvents dichloromethane and acetonitrile, as well as under methanolysis conditions reveals the nature of several species formed in solution. The key reactions are (I) ligand exchange involving either CH3CN or CH3OH, or, in IR experiments, bromide ions from KBr, (II) coordination-dissociation equilibria involving the urethane protecting groups of amino acid substituted ligands Boc-Xaa-bpa (Boc = tert-butoxycarbonyl, Xaa = glycine, alanine, and leucine, respectively, bpa = bis(picolyl)amine), (III) dissociation of a chloro ligand from LCuCl2 complexes and formation of square-pyramidal complex cations [LCuCl]+, and finally (IV) complete dissociation of the polydentate tertiary amide ligand to produce free copper ions in solution. Taken together, the results provide a fairly detailed qualitative picture of the processes which accompany the amide bond methanolysis.
authors.affiliation: Institut für anorganische Chemie, Universität Freiburg, Albertstrasse 21, 79104, Freiburg, Germany.
authors.forename: Nicole
authors.initials: N
authors.lastname: Niklas
authors.forename: Ralf
authors.initials: R
authors.lastname: Alsfasser