Synthesis and crystal structures of cationic lanthanide (III) monoporphyrinate complexes

摘要

Reactions of an excess of Ln[N(SiMe_3)_2]_3 centre dot x[LiCl(THF)_3], generated in situ from the reaction of anhydrous LnCl_3 with 3 equivalents of Li[N(SiMe_3)_2] in tetrahydrofuran, with 5, 10, 15, 20-tetrakis(p-methoxyphenyl) porphyrin (H_2TMPP) in refluxing tetrahydrofuran-bis(2-methoxyethyl)ether solution (1:6 v/v) gave the cationic mono-porphyrinate complexes [Ln~(III)(TMPP)(H_2O)_3]Cl (Ln=Yb; 1, Er, 2, or Y 3), and with 5, 10, 15, 20-tetrakis (p-tolyl)-porphyrin (H_2TPP) gave [Yb~(III)(TPP)(H_2O)_2(THF)]Cl 4. The structures of compounds 1-4 have been established by X-ray crystallography. Metathesis of 1 with an excess of AgBF_4 gave the unexpected neutral monoporphyrinate complex [Ag~(II)(TMPP)] 5 whose structure was also determined. Compound 1 catalysed the cyclotrimerization of phenyl isocyanate.