On the Question of Site‐Selective Ligand Exchange in Carboxylate‐Substituted Metal Oxo Clusters. Issue 17 (19th May 2015)

• Record Type: Journal Article
• Authors: Kreutzer, Johannes; Czakler, Matthias; Puchberger, Michael; Pittenauer, Ernst; Schubert, Ulrich
• Is Part Of: European journal of inorganic chemistry. Issue 17(2015)
• Page Start: 2889
• Page End: 2894
• Publication Date: 2015-05-19
• Subjects: Cluster compounds -- Ligand exchange -- Zirconium -- Titanium; Chemistry, Inorganic -- Periodicals; Organometallic chemistry -- Periodicals; Bioinorganic chemistry -- Periodicals; Solid state chemistry -- Periodicals; 546
• DOI: 10.1002/ejic.201500193
• Languages: English
• ISSNs: 1434-1948

Abstract

Abstract: Reaction of [Ti4 Zr4 O6 (OBu)4 (OMc)16 ] (OMc = methacrylate) with acetylacetone (acacH) resulted in dissection of the cluster and formation of [Ti(OBu)2 (acac)2 ] and the smaller cluster [Ti2 Zr4 O4 (OMc)16 ]. In contrast, the same reaction with [Zr6 O4 (OH)4 (OOCR)12 ]2 · 6RCOOH (R = Et, CH2 CH=CH2 ) led to site‐selective substitution of two carboxylate ligands and formation of isostructural [Zr6 O4 (OH)4 (OOCR)12– x (acac) x ]2 · 6RCOOH ( x ≤ 1). Abstract : The question of cluster degradation upon ligand exchange was probed for reactions of [Ti4 Zr4 O6 (OBu)4 (OMc)16 ] (OMc = methacrylate) and [Zr6 O4 (OH)4 (OOCR)12 ]2 · 6RCOOH with acetylacetone (acacH). A [Ti(OBu)2 (acac)2 ] unit was dissected from the bimetallic Ti/Zr cluster, while site‐selective substitution of two carboxylate ligands occurred in the latter cluster.