Retention of the cluster core structure during ligand exchange reactions of carboxylato-substituted metal oxo clusters

Abstract

The exchange of the carboxylato ligands of Zr4O2(methacrylato)12 in reactions with carboxylic acids proceeds with retention of the composition and structure of the cluster core. This was concluded from exchange/re-exchange experiments and from comparison of the IR bands of the cluster core of the original and ligand-exchanged clusters. The IR bands were assigned on the basis of DFT calculations. Scrambling reactions between two Zr4O2(OOCR)12 clusters with different carboxylato ligands are a new way to prepare mixed-ligand oxo clusters. Ligand exchange in Zr4O2(OOCR)12 clusters proceeds with retention of the cluster core. A new scrambling reaction is introduced for the preparation of mixed-ligand clusters.