Can the clusters Zr6O4(OH)4(OOCR)12 and [Zr6O4(OH)4(OOCR)12]2 be converted into each other?

Upon reaction of zirconium alkoxides, Zr(OR)4, with carboxylic acids, the clusters Zr6O4(OH)4(OOCR)12 (Zr6) or [Zr6O4(OH)4(OOCR)12]2 (Zr12) were obtained, depending on the employed carboxylic acid. The structures of Zr12 clusters with acetate, propionate, vinyl acetate or 3,3-dimethylacrylate ligands were determined by single-crystal X-ray diffraction, as well as that of methacrylate/acetate and methacrylate/ propionate mixed-ligand clusters. The structure of the hafnium cluster [Hf6O4(OH)4(acetate)12]2 is also reported for comparison. The Zr12 clusters are structurally related to the Zr6 clusters since they are composed of two Zr6 sub-units which are bridged by four carboxylate ligands. In each compound, carboxylic acid molecules interact with the cluster by hydrogen bonding to part of the ?3-OH ligands. The clusters are highly dynamic in solution, due to site exchange of the Introduction We have previously prepared a variety of carboxylatesubstituted titanium and zirconium oxo clusters, mainly to use the (meth)acrylate derivatives for the preparation of cluster-crosslinked polymers.[1] During this work, we obtained several types of zirconium oxo clusters, among them Zr6O4(OH)4(OOCR)12 (Zr6) and the dimer [Zr6O4(OH)4- (OOCR)12]2 (Zr12), having the same overall stoichiometry. Previous to this work, we obtained crystalline Zr6 clusters for RCOO = methacrylate (1)[2] and 5-norbornene-2-carboxylate,[ 3] and the Zr12 type for RCOO = acrylate.[4] The crystal structures of both cluster types additionally contain carboxylic acid molecules interacting with the ligand shell of the clusters by hydrogen bonding (see below). The Zr6 clusters consist of a Zr6O4(OH)4 cluster core in which the triangular faces of a Zr6 octahedron are alternatively capped by ?3-O and ?3-OH groups. The structure of the Zr12 cluster consists of two Zr6 sub-units which are connected by four carboxylate bridges. This will be discussed below in more detail. In a formal manner, the Zr12 [a] Institute of Materials Chemistry, Vienna University of Technology, Getreidemarkt 9/165, 1060 Wien, Austria [?] Current address: Department of Chemical Sciences, University of Padova, Via Marzolo 1, 35131 Padova, Italy Eur. J. Inorg. Chem. 2006, 3283-3293 © 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 3283 carboxylate ligands; low-temperature NMR spectra of the clusters correspond to the solid-state structures. The Zr6 and Zr12 clusters can be clearly distinguished by their solution NMR spectra. Reactions between selected Zr12 clusters and carboxylic acids led to the conclusion, that only part of the ligands is accessible for ligand exchange reactions. In contrast, all ligands were exchanged when the Zr6 cluster Zr6O4(OH)4(methacrylate)12 was treated with an excess of propionic acid, and Zr6O4(OH)4(propionate)12 was formed. However, the Zr12 cluster [Zr6O4(OH)4(propionate)12]2 was obtained from the reaction of Zr(OBu)4 with propionic acid. The Zr6 and Zr12 clusters thus do not interconvert at the given reaction conditions.