Synthesis and Characterization of Rhenium(V) Oxo Complexes Bearing PNP-Pincer Ligands

The synthesis of a series of pyridine-based PNP-pincer rhenium-oxo complexes, with phenyl (1, 3), tert-butyl (2), or cyclohexyl (4) groups on the phosphorus atoms and either a ReO2X (1, 2) or a ReCl2O (3, 4) core is reported. The structures of these compounds were characterized using 1H, 13C, and 31P NMR and using X-ray crystallography for 1 and 4. Compounds 2 and 3 crystallize as the corresponding ReO­(OH)­X compounds upon their reaction with moisture during the crystallization process. The complexes were tested as catalysts in the oxidation reaction of limonene with H2O2, the oxygen atom transfer reaction from pyridine N-oxide to triphenylphosphine, and the dehydration reaction of 1-phenylethanol, but all showed poor catalytic performance. All complexes can be deprotonated at the benzylic arm, and 2 can be deprotonated twice, accompanied by dearomatization of the pyridine ring. 3 and 4 are highly stable in their oxidized forms. The noninnocent behavior shown here could open up possibilities for cooperative catalysis.