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

Reactions of an excess of Ln[N(SiMe3)(2)](3). x[LiCl(THF)(3)], generated in situ from the reaction of anhydrous LnCl(3) with 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 [Ln(III)(TMPP)(H2O)(3)]Cl (Ln = Yb; 1, Er, 2, or Y 3), and with 5,10,15,20-tetrakis(p-tolyl)porphyrin (H2TTP) gave [Yb-III(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 AgBF4 gave the unexpected neutral monoporphyrinate complex [Ag-II(TMPP)] 5 whose structure was also determined. Compound 1 catalysed the cyclotrimerization of phenyl isocyanate.