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In Situ Assembly, De‐Metalation and Induced Repair of a Copper‐Polyoxovanadate Oxidation Catalyst
Author(s) -
Kastner Katharina,
Lechner Manuel,
Weber Stefan,
Streb Carsten
Publication year - 2017
Publication title -
chemistryselect
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.437
H-Index - 34
ISSN - 2365-6549
DOI - 10.1002/slct.201701321
Subject(s) - catalysis , copper , chemistry , metalation , vanadium , redox , vanadium oxide , yield (engineering) , in situ , inorganic chemistry , oxide , organic chemistry , materials science , metallurgy
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 [(Me 2 NH 2 )Cu(MeCN)V 12 O 32 Cl] 2− : the catalyst self‐assembles by reaction of Cu II and [(Me 2 NH 2 ) 2 V 12 O 32 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.