Ligand‐Unsupported Cuprophilicity in the Preparation of Dodecacopper(I) Complexes and Raman Studies

Synthesis and characterization of two dodecacopper(I) extended metal atom chains (EMAC) assembled by two hexadentate bis(pyridylamido)amidinate‐supported hexacopper(I) string complexes (monomers) via the ligand‐unsupported cuprophilicity are described. In addition to short unsupported Cu−Cu contacts, two hexacopper fragments in these two dodecacopper EMACs show a bent conformation based on X‐ray crystallography. Compared with their THF‐bound hexacopper(I) monomers and protonated ligands, these ligand‐unsupported cuprophilic interactions are shown to be weak by Raman spectroscopy. DFT calculations suggest the ligand‐unsupported cuprophilicity originate from weak attractive orbital interactions, and the strength is estimated to be 2.4 kcal mol−1. Ketten mit vielen Gliedern: Zwei Dodekakupfer(I)‐Ketten wurden hergestellt, in denen sich zwei gebogene strangförmige Hexakupfer(I)‐Komplexe über kurze nichtverbrückte Cu‐Cu‐Kontakte zusammenlagern. Diese schwachen cuprophilen Wechselwirkungen wurden Raman‐spektroskopisch und anhand von Dichtefunktionalrechnungen bestätigt.