Coordination Chemistry of Nitrile and Amino Pendant Arm Derivatives of [9]aneN 2 S and [9]aneNS 2 with Pd II and Cu II

Palladium( II ) and copper( II ) complexes [Pd( L 1 )Cl 2 ], [Pd( L 3 )Cl 2 ], [Cu( L 1 )Cl 2 ], [Cu( L 3 )Cl 2 ], [Pd( L 2 )][BF 4 ] 2 , [Pd( L 4 )Cl]BF 4 , [Cu( L 2 )][NO 3 ] 2 and [Cu( L 4 )Cl]PF 6 of the nitrile ( L 1 and L 3 ) and amino ( L 2 and L 4 ) pendant arm derivatives of 1‐thia‐4,7‐diazacyclononane ([9]aneN 2 S) and 7‐aza‐1,4‐dithiacyclononane ([9]aneNS 2 ) have been prepared and fully characterised. In each case, a square‐pyramidal coordination sphere is observed at both metal ions with either one or two Cl − anions completing the donor set. The tridentate nine‐membered macrocyclic moiety adopts a [333] conformation in all the complexes obtained. The five‐membered chelate rings involving the donor atoms of the basal plane adopt a gauche configuration with very similar degrees of puckering. The “innocent” nitrile pendant arms in L 1 and L 3 do not bind to the metal ions, but still appear to influence the binding of the tridentate macrocyclic frameworks via the tertiary amine sites. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)