New 4-Coordinate copper (II) and zinc (II) complexes useful as catalysts for oxidation of alcohols and amines

摘要

4-Coordinate copper (II) and zinc (II) complexes which include one ligand L per metal atom, are new. 4-Coordinate copper (II) and zinc (II) complexes which include one phenoxy (or phenoxy radical) ligand L per metal atom. H2L is of formula (III): Q = S, O, N(R3), P(R4) or NH-Ph'-NH; R1, R2 = a radical-stabilizing residue, especially an alkyl group which has a tertiary C atom linked to the phenyl ring; R3, R4 = H or 1-6C alkyl; Ph = 1,2-phenylene Independent claims are included for: (A) The preparation method of complexes as described above, comprising: (a) reaction of a copper or zinc salt with a compound of formula (III), in a ratio of at least one mole of ligand per gram-atom of metal, in a dry, oxygen-free solvent (especially methanol or an ether), in the presence of at least 2 gram-equivalents of a nitrogen-containing base B per gram-atom of metal, at 20-100 deg C, under an inert gas atmosphere; (b) contacting the resulting solution with dry oxygen or with a dry gas which contains oxygen; and (c) separation of the resulting precipitate; and (B) Oxidation of an organic substrate (which is a primary or secondary alcohol or amine) with oxygen, comprising addition of a copper (II) or zinc (II) complex as described above as an oxidation catalyst, or formation of such a catalyst in situ (as described in steps (a) and (b) of process (A) above), and contacting the substrate with oxygen or an oxygen-containing gas, in the presence of the catalyst, in a dry solvent.