G. Speier, Jozsef Csihony, A. Whalen
Jun 5, 1996
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3
Influential Citations
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Journal
Inorganic Chemistry
Abstract
Stoichiometric quantities of 3,5-di-tert-butylcatechol and aqueous ammonia react in pyridine solution to form 2-amino-4,6-di-tert-butylphenol. Under an atmosphere of dioxygen the aminophenol is oxidized to either the corresponding iminosemiquinone or iminobenzoquinone. In the presence of Cu(II) iminosemiquinone condensation with the aminophenol gives the Cat-N-SQ radical ligand obtained as the Cu(py)2(Cat-N-SQ) complex. Metal and ligand magnetic orbitals are orthogonal and couple ferromagnetically to give a S = 1 molecular spin state at temperatures up to 300 K. In nonpolar solvents the complex undergoes ligand oxidation and disproportionation to give Cu(Cat-N-BQ)2. Crystallographic characterization on crystals obtained as the i-propanol solvate [orthorhombic, C2221, a = 19.548(3) A, b = 24.536(5) A, c = 23.655(5) A, V = 11346(4) A3, Z = 8, R = 0.068] show that the expected Jahn−Teller distortion appears in the trans Cu−O lengths of the equatorial plane rather than for the axial Cu−N lengths. Reactions ca...