US EPA

5036369 

Journal Article 

Aerobic Oxidation Catalysis by a Molecular Barium Vanadium Oxide 

Lechner, M; Kastner, K; Chan, CJ; Güttel, R; Streb, C 

2018 

Yes 

Chemistry: A European Journal
ISSN: 0947-6539
EISSN: 1521-3765 

WILEY-V C H VERLAG GMBH 

WEINHEIM 

24 

19 

4952-4956 

English 

29438588 

10.1002/chem.201706046 

WOS:000429414100031 

https://search.proquest.com/scholarly-journals/aerobic-oxidation-catalysis-molecular-barium/docview/2023051982/se-2?accountid=171501
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Aerobic catalytic oxidations are promising routes to replace environmentally harmful oxidants with O2 in organic syntheses. Here, we report a molecular barium vanadium oxide, [Ba4 (dmso)14 V14 O38 (NO3 )] (={Ba4 V14 }) as viable homogeneous catalyst for a series of oxidation reactions in N,N-dimethyl formamide solution under oxygen (8 bar). Starting from the model compound 9,10-dihydroanthracene, we report initial dehydrogenation/ aromatization leading to anthracene formation; this intermediate is subsequently oxidized by stepwise oxygen transfer, first giving the mono-oxygenated anthrone and then the di-oxygenated target product, anthraquinone. Comparative reaction analyses using the Neumann catalyst [PV2 Mo10 O40 ]5- as reference show that oxygen diffusion into the reaction mixture is the rate-limiting step, resulting in accumulation of the reduced catalyst species. This allows us to propose improved reactor designs to overcome this fundamental challenge for aerobic oxidation catalysis. 

Chemistry; catalysis; oxidation; polyoxometalate; polyoxovanadate; self-assembly; Anthracene; Oxidants; Vanadium; Vanadium oxides; Dehydrogenation; Oxygen transfer; Oxidizing agents; Anthraquinone; Diffusion rate; Oxygenation; Catalysts; Dimethyl formamide