The weak-link approach has been employed to synthesize a series of bimetallic Cu(I) macrocycles in high yield. Addition of phosphinoalkylether or -thioether ligands to [Cu(MeCN)4]PF6 produces "condensed" intermediates, [μ-(1,4-(PPh2CH 2CH2X)2Y2)Cu2][PF 6]2 (X = S, O; Y = C6H4, C 6F4), containing strong P-Cu bonds and weaker O-Cu or S-Cu bonds. The weak bonds of these intermediates can be cleaved through ligand substitution reactions to generate macrocyclic structures, [μ-(1,4-(PPh 2CH2CH2X)2Y)2(Z) nCu2][PF6]2 (X = S, O; Y = C 6H4, C6F4; Z = pyridine, acetonitrile, diimines, isocyanide) in nearly quantitative yields. The incorporation of tetrahedral Cu(I) metal centers into these macrocycles provides a pathway to complexes that differ from analogous d8 square planar macrocycles generated via this approach in their increased air stability, small molecule reactivity, and ability to form multiple structural isomers. Solid-state structures, as determined by single-crystal X-ray diffraction studies, are presented for condensed intermediates and an open macrocycle.
ASJC Scopus subject areas
- Physical and Theoretical Chemistry
- Inorganic Chemistry