The complexation of the mixed aza–thioether crown 2,5,8-trithia[9](2,9)-1,10-phenanthrolinophane (L) with PdII, PtII and RhIII has been investigated. The single-crystal structures of [PdL][PF6]2 and [PtL][PF6]2 confirm [N2S2 + S] co-ordination in both complexes with the ligand adopting a folded conformation. Carbon-13 NMR spectroscopic studies, carried out in the solid state as well as in solution, indicated that only one form of each complex is present in solution, having [N2S2 + S] co-ordination at PdII and PtII and octahedral co-ordination [N2S3 + Cl–] at RhIII in [RhL(Cl)]2+. The redox properties of [ML][PF6]2 (M = Pd or Pt) in MeCN are reported.
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
ISAIA, FRANCESCO;LIPPOLIS, VITO;
1997-01-01
Abstract
The complexation of the mixed aza–thioether crown 2,5,8-trithia[9](2,9)-1,10-phenanthrolinophane (L) with PdII, PtII and RhIII has been investigated. The single-crystal structures of [PdL][PF6]2 and [PtL][PF6]2 confirm [N2S2 + S] co-ordination in both complexes with the ligand adopting a folded conformation. Carbon-13 NMR spectroscopic studies, carried out in the solid state as well as in solution, indicated that only one form of each complex is present in solution, having [N2S2 + S] co-ordination at PdII and PtII and octahedral co-ordination [N2S3 + Cl–] at RhIII in [RhL(Cl)]2+. The redox properties of [ML][PF6]2 (M = Pd or Pt) in MeCN are reported.
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