Amavadin and Other Vanadium Complexes as Remarkably Efficient Catalysts for One‐Pot Conversion of Ethane to Propionic and Acetic Acids

Abstract Synthetic amavadin Ca[V{ON[CH(CH 3 )COO] 2 } 2 ] and its models Ca[V{ON(CH 2 COO) 2 } 2 ] and [VO{N(CH 2 CH 2 O) 3 }], in the presence of K 2 S 2 O 8 in trifluoroacetic acid (TFA), exhibit remarkable catalytic activity for the one‐pot carboxylation of ethane to propionic and acetic acids with the former as the main product (overall yields up to 93 %, catalyst turnover numbers (TONs) up to 2.0×10 4 ). The simpler V complexes [VO(CF 3 SO 3 ) 2 ], [VO(acac) 2 ] and VOSO 4 are less active. The effects of various factors, namely, C 2 H 6 and CO pressures, time, temperature, and amounts of catalyst, TFA and K 2 S 2 O 8 , have been investigated, and this allowed optimisation of the process and control of selectivity. 13 C‐labelling experiments indicated that the formation of acetic acid follows two pathways, the dominant one via oxidation of ethane with preservation of the CC bond, and the other via rupture of this bond and carbonylation of the methyl group by CO; the CC bond is retained in the formation of propionic acid upon carbonylation of ethane. The reactions proceed via both C‐ and O‐centred radicals, as shown by experiments with radical traps. On the basis of detailed DFT calculations, plausible reaction mechanisms are discussed. The carboxylation of ethane in the presence of CO follows the sequential formation of C 2 H 5 . , C 2 H 5 CO . , C 2 H 5 COO . and C 2 H 5 COOH. The C 2 H 5 COO . radical is easily formed on reaction of C 2 H 5 CO . with a peroxo V catalyst via a V{η 1 ‐OOC(O)C 2 H 5 } intermediate. In the absence of CO, carboxylation proceeds by reaction of C 2 H 5 . with TFA. For the oxidation of ethane to acetic acid, either with preservation or cleavage of the CC bond, metal‐assisted and purely organic pathways are also proposed and discussed.