Synthesis and Coordination Chemistry of Novel Binucleating Macrocyclic Ligands with Amine-thioether and Amine-thiophenolate Donor Functions

Z. Naturforsch. 56 b, 901-907 (2001); received June 5, 2001 Macrocyclic Ligands, Nitrogen, Sulfur The ability of the aromatic tetraaldehyde l,2-bis(4-rm-butyl-2,6-diformylphenylsulfanyl)ethane (1 ) to function as a precursor in the preparation of binucleating hexaamine-dithiolate lig­ ands has been investigated. Reductive amination of compound 1 with bis(aminoethyl)amine un­ der medium-dilution conditions affords the macrobicyclic hexaamine-dithioether compound L 1. Deprotection of the [1+2] condensation product gives the corresponding 24-membered hexaamine-dithiophenol ligand H2 L2. The formulation of L 1 as a macrobicyclic amine-thioether was confirmed by an X-ray crystal structure determination of the tetranuclear nickel(II) complex of L 1, [{(L jN iiC lili^ -C l^K B Ph;) (2b). The formulation of the doubly deprotonated form (L2)2of H2 L2 as a 24-membered amine-thiophenolate ligand was confirmed by an X-ray crystal structure determination of the dinuclear cobalt(III) complex, [(L2 )Com(^-OH)](C1 0 4 ) 2 • Cl (3). The preparation and the crystal structures of the new compounds are described.