Synthesis and Oxidation Catalysis of [Tris(oxazolinyl)borato]cobalt(II) Scorpionates

Abstract

The reaction of CoCl 2 · THF and thallium tris(4,4‐dimethyl‐2‐oxazolinyl)phenylborate (TlTo M ) in tetrahydrofuran (THF) provides To M CoCl ( 1 ) in 95 % yield; however, appropriate solvents and starting materials are required to favor 1 over two other readily formed side‐products, (To M ) 2 Co ( 2 ) and {HTo M }CoCl 2 ( 3 ). ESR, NMR, FTIR, and UV/Vis spectroscopies were used to distinguish these cobalt(II) products and probe their electronic and structural properties. Even after the structures indicated by these methods were confirmed by X‐ray crystallography, the spectroscopic identification of trace contaminants in the material was challenging. The recognition of possible contaminants in the synthesis of To M CoCl in combination with the paramagnetic nature of these complexes provided impetus for the utilization of X‐ray powder diffraction to measure the purity of the To M CoCl bulk sample. The X‐ray powder diffraction results provide support for the bulk‐phase purity of To M CoCl in preparations that avoid 2 and 3 . Thus, 1 is a precursor for new [tris(oxazolinyl)borato]cobalt chemistry, as exemplified by its reactions with KO t Bu and NaOAc to give To M CoO t Bu ( 4 ) and To M CoOAc ( 5 ), respectively. Compound 5 is a catalyst for the oxidation of cyclohexane with meta ‐chloroperoxybenzoic acid ( m CPBA), and the rate constants and selectivity for cyclohexanol versus cyclohexanone and ε‐caprolactone were assessed.