Cp*Rh-Based Heterometallic Metallarectangles: Size-Dependent Borromean Link Structures and Catalytic Acyl Transfer

A series of Cp*Rh-based functional metallarectangles have been synthesized from metallaligands. Enlargement of one linker leads to the isolation of two novel Borromean link architectures. All these complexes are intact in solution, as evident from ESI-MS spectroscopic analysis. Arising from the combination of open Cu centers and favorable cavity space, {(Cp*Rh)4­(bpe)2­[Cu­(opba)·​2MeOH]2}­4­(OTf)·​6MeOH shows extraordinary catalytic abilities with high efficiency and wide substrate selectivity in the acyl-transfer reaction.