Retrosynthetic Analysis Applied to Clip-off Chemistry: Synthesis of Four Rh(II)-Based Complexes as Proof-of-Concept

Angew Chem Int Ed Engl. 2023 Nov 27;62(48):e202310354. doi: 10.1002/anie.202310354. Epub 2023 Sep 19.

Abstract

Clip-off Chemistry is a synthetic strategy that our group previously developed to obtain new molecules and materials through selective cleavage of bonds. Herein, we report recent work to expand Clip-off Chemistry by introducing into it a retrosynthetic analysis step that, based on virtual extension of the products through cleavable bonds, enables one to define the required precursor materials. As proof-of-concept, we have validated our new approach by synthesising and characterising four aldehyde-functionalised Rh(II)-based complexes: a homoleptic cluster; a cis-disubstituted paddlewheel cluster; a macrocycle; and a crown.

Keywords: Bond Breaking; Clip-off Chemistry; Disassembly; Metal-Organic Polyhedra; Retrosynthetic Analysis.