Single‐Pot Ethane Carboxylation Catalyzed by New Oxorhenium(V) Complexes with N,O Ligands

The oxorhenium(V) chelates [ReOCl(N,O‐L)(PPh₃)] [N,O‐L=(OCH₂CH₂)N(CH₂CH₂OH)(CH₂COO) ( 2 ), (OCH₂CH₂)N(CH₂COO)(CH₂COOCH₃) ( 3 )] and [ReOCl₂(N,O‐L)(PPh₃)] [N,O‐L=C₅H₄N(COO‐2) ( 4 ) C₅H₃N(COOCH₃‐2)(COO‐6) ( 5 )] have been prepared by reaction of [ReOCl₃(PPh₃)₂] ( 1 ), in refluxing methanol, with N,N‐bis(2‐hydroxyethyl)glycine [bicine; N(CH₂CH₂OH)₂(CH₂COOH)], N‐(2‐hydroxyethyl)iminodiacetic acid [N(CH₂CH₂OH)(CH₂COOH)₂], picolinic acid [NC₅H₄(COOH‐2)] or 2,6‐pyridinedicarboxylic acid [NC₅H₃(COOH‐2,6)₂], respectively, with ligand esterification in the cases of 3 and 5 . All these complexes have been characterized by IR and multinuclear NMR spectroscopy, FAB⁺‐MS, elemental and X‐ray diffraction structural analyses. They act as catalysts, in a single‐pot process, for the carboxylation of ethane by CO, in the presence of potassium peroxodisulfate K₂S₂O₈, in trifluoroacetic acid (TFA), to give propionic and acetic acids, in a remarkable yield (up to ca. 30%) and under relatively mild conditions, with some advantages over the industrial processes. The picolinate complex 4 provides the most active catalyst and the carboxylation also occurs, although much less efficiently, by the TFA solvent in the absence of CO. The selectivity can be controlled by the ethane and CO pressures, propionic acid being the dominant product for pressures about ca. 7 and 4 atm, respectively (catalyst 4 ), whereas lower pressures lead mainly to acetic acid in lower yields. These reactions constitute an unprecedented use of Re complexes as catalysts in alkane functionalization.