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Title: Synthesis and oxidation catalysis of [tris(oxazolinyl)borato]cobalt(II) scorpionates

The reaction of CoCl2·THF and thallium tris(4,4-dimethyl-2-oxazolinyl)phenylborate (TlToM) in tetrahydrofuran (THF) provides ToMCoCl (1) in 95 % yield; however, appropriate solvents and starting materials are required to favor 1 over two other readily formed side-products, (ToM)2Co (2) and {HToM}CoCl2 (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 ToMCoCl 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 ToMCoCl bulk sample. Furthermore, the X-ray powder diffraction results provide support for the bulk-phase purity of ToMCoCl 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 KOtBu and NaOAc to give ToMCoOtBu (4) and ToMCoOAc (5), respectively. Compound 5 is a catalyst for the oxidation of cyclohexane with meta-chloroperoxybenzoic acid (mCPBA), and the rate constants and selectivity for cyclohexanol versus cyclohexanone and ϵ-caprolactone were assessed.
 [1] ;  [2] ;  [1] ;  [1] ;  [2] ;  [2] ;  [2] ;  [2] ;  [1] ;  [2] ;  [3] ;  [1]
  1. Ames Lab. and Iowa State Univ., Ames, IA (United States)
  2. Iowa State Univ., Ames, IA (United States)
  3. Ames Lab., Ames, IA (United States)
Publication Date:
OSTI Identifier:
Report Number(s):
Journal ID: ISSN 1434-1948
Grant/Contract Number:
Accepted Manuscript
Journal Name:
European Journal of Inorganic Chemistry
Additional Journal Information:
Journal Name: European Journal of Inorganic Chemistry; Journal ID: ISSN 1434-1948
ChemPubSoc Europe
Research Org:
Ames Laboratory (AMES), Ames, IA (United States)
Sponsoring Org:
Country of Publication:
United States
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY scorpionates; oxazolines; cobalt; structure elucidation; oxidation