Synthesis, characterization and crystal structures of neutral mono- and di-nuclear lanthanide(III) porphyrinate complexes

Abstract

The interaction of 5,10,15,20-tetrakis(p-tolyl)porphyrin (H₂TTP) and 5,10,15,20-tetraphenylporphyrin (H₂TPP) with an excess of Y^III[N(SiMe₃)₂]₃·x[LiCl(THF)]₃, generated in situ, in refluxing bis(2-methoxyethyl) ether gave the neutral monoporphyrinate complexes [Y^III(TTP)(Cl){(CH₃OCH₂CH₂)₂O}] 1 and [Y^III(TPP)(Cl)(H₂O)(THF)] 2, respectively. However, the interaction of 5,10,15,20-tetrakis(p-methoxyphenyl)porphyrin (H₂TMPP), H₂TTP and H₂TPP with an excess of Yb^III(NPh₂)₃·x[LiCl(THF)₃], generated in situ, in refluxing bis(2-methoxyethyl) ether gave the neutral hydroxide-bridged dinuclear porphyrinate complexes [{Yb^III(TMPP)(µ-OH)}₂] 3 and [{Yb^III(TTP)}₂(µ-OH)(µ-OCH₂CH₂OCH₃)] 4, and the neutral monoporphyrinate complex [Yb^III(TPP)(Cl)(H₂O)(THF)] 5, respectively. The structures of these five complexes have been established by X-ray crystallography.