We have prepared 1,8-naphthyridines substituted at the 2,7 positions with imine groups; these compounds, substituted with various N-alkyl and N-aryl groups, constitute tetradentate chelating ligands, N4L. Iodo and bromo-bridged dicopper(I) complexes N4LCu2X2 react with mercaptans in methanol to give green solids (60-70% yield), the 1H-NMR spectra of which are consistent with the presence of bridging mercaptides between two copper(I) sites. Upon standing in the mother liquor for several weeks, dark red-brown crystals formed. A crystal structure revealed a molecular compound comprising two naphthyridine-diimine dicopper(I) bridging mercaptide N4LCu2(SR)2 subunits; these are further bridged by the mercaptides to an unusual Cu4I4 center in which each of the four "central" coppers bears a terminal iodide ligand. The copper(I)-copper(I) distances of this compound are quite short, ranging from ca. 2.7 angstroms (subunit) to ca. 3.0 angstroms (central). Synthesis, spectroscopy, structure and reactivity of this and related mercaptide-bridged dicopper(I) complexes will be presented.

Mercaptide-bridged dicopper(I) naphthyridine-diimine complexes bearing short metal-metal distances

254th National Meeting (2017)

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