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Department of Inorganic Chemistry, Indian Association for the Cultivation of Science, 2A & 2B Raja S. C. Mullick Road, Jadavpur, India
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Dalton Trans., 2012,41, 11476-11481
25 May 2012,
31 Jul 2012
First published online
03 Aug 2012
Five copper complexes [(L1)2Cu(H2O)](ClO4)2 (1), [(L1)Cu(H2O)3](ClO4)2 (1a), [(L3)2Cu(H2O)](ClO4)2 (2), [(L5)2Cu(H2O)](ClO4)2 (3) and [(L6)2Cu](ClO4) (4) (where L1 = 1,10-phenanthroline, L3 = 1,10-phenanthroline-5,6-dione, L5 = 1,10-phenanthrolinefuroxan and L6 = 2,9-dimethyl-1,10-phenanthrolinefuroxan), and in situ prepared copper complexes of 2,9-dimethyl-1,10-phenanthroline (L2) or 2,9-dimethyl-1,10-phenanthrolinedione (L4) were used for aerial oxidation of primary alcohols to the corresponding aldehydes under ambient conditions. The copper catalysts have been found to catalyze a series of primary alcohols including one secondary alcohol with moderate turnover numbers and selectivity towards primary alcohols. Copper(II) complexes 1 (or 1a) and 2 were found to be the better catalysts among all other systems explored in this study. A copper(II)-superoxo species is implicated to initiate the oxidation reaction. Structural and electronic factors of 1,10-phenanthroline-based ligands affecting the catalytic results for aerial oxidation of alcohols are discussed.
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