CONFORMATIONALLY LOCKED MIXED AZA-THIOETHER MACROCYCLES - SYNTHESIS AND STRUCTURES OF COMPLEXES OF PD-II, PT-II AND RH-III OF 2,5,8-TRITHIA-[9](2,9)-1,10-PHENANTHROLINOPHANE

The complexation of the mixed aza-thioether crown 2,5,8-trithia[9](2,9 )-1,10-phenanthrolinophane (L) with Pd-II, Pt-II and Rh-III has been i nvestigated. The single-crystal structures of [PdL][PF6](2) and [PtL][ PF6](2) confirm [N2S2 + S] co-ordination in both complexes with the li gand adopting a folded conformation. Carbon-13 NMR spectroscopic studi es, carried out in the solid State as well as in solution, indicated t hat only one form of each complex is present in solution, having [N2S2 + S] co-ordination at Pd-III and Pt-II and octahedral co-ordination [ N2S3 + Cl-] at Rh-III in [RhL(Cl)](2+). The redox properties bf [ML][P F6](2) (M = Pd or Pt) in MeCN are reported.