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

Reactions of an excess of Ln[N(SiMe3)2]3·x[LiCI(THF)3], generated in situ from the reaction of anhydrous LnCl3with 3 equivalents of Li[N(SiMe3)2] in tetrahydrofuran, with 5,10,15,20-tetrakis(p-methoxyphenyl)porphyrin (H2TMPP) in refluxing tetrahydrofuran-bis(2-methoxyethyl) ether solution (1:6 v/v) gave the cationic monoporphyrinate complexes [Ln111(TMPP)(H2O)3]Cl (Ln = Yb; 1, Er, 2, or Y 3), and with 5,10,15,20-tetrakis(p-tolyl)-porphyrin (H2TTP) gave [Yb111(TTP)(H2O)2(THF)]Cl 4. The structures of compounds 1-4 have been established by X-ray crystallography. Metathesis of 1 with an excess of AgBF4gave the unexpected neutral monoporphyrinate complex [Ag11(TMPP)] 5 whose structure was also determined. Compound 1 catalysed the cyclotrimerization of phenyl isocyanate.