In Situ Assembly, De‐Metalation and Induced Repair of a Copper‐Polyoxovanadate Oxidation Catalyst. Issue 20 (11th July 2017)

• Record Type: Journal Article
• Authors: Kastner, Katharina; Lechner, Manuel; Weber, Stefan; Streb, Carsten
• Is Part Of: ChemistrySelect. Volume 2:Issue 20(2017)
• Page Start: 5542
• Page End: 5544
• Publication Date: 2017-07-11
• Subjects: Metal Oxide -- Oxidation Catalysis -- Polyoxometalate -- Polyoxovanadate -- Self-Assembly; Chemistry -- Periodicals; 540.5
• DOI: 10.1002/slct.201701321
• Languages: English
• ISSNs: 2365-6549

Abstract

Abstract: Polyoxometalates (POMs) offer a rich dynamic solution chemistry so that in principle, the assembly and repair of POM oxidation catalysts in situ, i. e. under catalytic conditions, is possible. Here, we report the oxidative activity of a molecular copper vanadium oxide cluster [(Me2 NH2 )Cu(MeCN)V12 O32 Cl] 2− : the catalyst self‐assembles by reaction of Cu II and [(Me2 NH2 )2 V12 O32 Cl] 3− in solution and selectively oxidizes secondary alcohols (here: 1‐phenylethanol) to the corresponding ketones in near quantitative yield. The catalyst can be deactivated in solution by removal of the Cu II site from the catalyst. Subsequent catalyst re‐assembly is achieved by addition of Cu II ions, leading to the recovery of the catalytic activity. The system might serve as molecular model to study repair mechanism in POM catalysts with relevance for "green" oxidation processes. Abstract : A molecular copper vanadium oxide cluster is reported as selective alcohol‐to‐ketone oxidation catalyst under mild conditions. The solution chemistry of the catalyst is explored by triggering the in situ self‐assembly, de‐metalation and subsequent repair under catalytic conditions. The results demonstrate how molecular vanadium oxides can be used as dynamic oxidation catalysts for homogeneous substrate oxidations in solution.