The synthesis and characterization of a bis-oxime functionalized binucleating macrocycle and its polynuclear complexes

Summary A novel tetraoxime containing a substituted twofold macrocycle, 6,6-spirobi[1,12-di(hydroxyimino)-2,39,10-dibenzo-1, 11-diaza-4,8-dithiacyclotridecane] (5), has been synthesized from 6,6-bis(5-amino-3,4-benzo-2-thiapentyl)-1, 11-diamino-2, 39, 10-dibenzo-4,8-dithiaundecane (3), which was itself prepared from the potassium salt of 2-aminothiophenol (2), pentaerythrityltetrabromide (1) and cyanogendi-N-oxide (4). A polymeric Co^III complex of (5) containing a 11 metalligand ratio has been isolated. The template synthesis of a new Co^III complex containing bridging BF₂ groups was achieved using the hydrogen-bridged Co^III complex. The hetero-polynuclear complex of (5) was prepared by reacting the BF_inf2^sup–-capped polymeric Co^III complex with bis(benzonitrile)Pd^IIchloride. The structure of the ligand and its complexes are in accord to elemental analyses, ¹H- and ¹³C-n.m.r., i.r. and mass spectral data.