Yttrium(III) and lanthanide(III) perchlorate complexes with the 2,2,6,6- tetramethylpiperidine nitroxide free radical

Summary 2,2,6,6-Tetramethylpiperidine nitroxide free radical (TMPNO) complexes with Y³⁺ and Ln³⁺ (Ln = La, Ce, Pr, Nd, Sm, Eu, Gd, Dy, Ho, Er or Yb) perchlorates were synthesized and characterized by means of i.r. and e.s.r. spectral, magnetic susceptibility and molar conductance studies. The new complexes are of the general type M(TMPNO-)₂(OH₂)₃(OCIO₃)](ClO₄)₂ (M = Y or Ln), involving two TMPNO;, three aqua and one unidentate perchlorato ligand in the complex cation, and two anionic C10₄ groups. The NO bond-order in coordinated TMPNO is apparently two, as suggested by the i.r. evidence. The magnetic susceptibility and e.s.r. data were interpreted in terms of partial spin-spin coupling interaction between the unpaired electrons of the two TMPNO- ligands, as well as unpaired f electrons, in the case of paramagnetic lanthanide(Ill) ions. Severe steric hindrance, introduced during coordination of the free radical ligand through the NO oxygen atom, does not seem to allow accommodation of more than two TMPNO molecules in the inner coordination sphere of the central Y³⁺, or Ln³⁺ ion.To whom all correspondence should be directed.