851936-12-4Relevant articles and documents
Binucleating aza-sulfonate and aza-sulfinate macrocycles - Synthesis and coordination chemistry
Hausmann, Julia,Kaess, Steifen,Klod, Sabrina,Kleinpeter, Erich,Kersting, Berthold
, p. 4402 - 4411 (2007/10/03)
The preparation and ligating properties of S-oxygenated derivatives of a macrobinucleating hexaazadithiophenolate macrocycle H2L1 of the Robson type towards nickel(II) and zinc(II) ions are reported. Nickel complexes of the hexaazadiphenylsulfonate ligand (L2)2- [(L2)NiII2(μ-L)]+ (L = m-Cl-OBz- (3), Cl- (4) and OAc- (6)] are readily obtained in high yields by oxidation of the respective [(L 1)NiII2(μ-L)]+ parent complexes [L = m-Cl-OBz- (2), Cl- (1), OAc- (5)] with meta-chloroperoxybenzoic acid or hydrogen peroxide. Decomposition of the sulfonate complexes gives the free macrocycle H2L2 which, upon treatment with Zn(OAc)2·2H2O, produces the diamagnetic zinc complex [(L2)ZnII2(OAc)] + (8). A dinuclear CuII complex of the hexaazadisulfinate derivative (L3)2-, [(L3)CuII 2]2+ (9), is formed rather unexpectedly by air oxidation of (L1)2- in the presence of CuI. The crystal-structure determinations of the perchlorate or tetraphenylborate salts of 2,3, and 4 show that the new ligands support the formation of binuclear complexes with bowl-shaped, calixarene-like binding cavities. NMR spectroscopic studies of 8 show that the complexes retain their solid-state structures in solution. A crystal-structure determination of 9 reveals two five-coordinate CuII ions bridged by the two sulfinate functions of (L 3)2-. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004.
