Two-phosphonate Catalytic Mannich Reaction, Together With The Rare Earth Metals

The ligands involving phosphoryl (P=O) group are favorable to coordinate to lanthanide ions and actinide ions, and have been applied in the solvent extract and separation process. The syntheses, structures and catalysis properties of rare earth complexes and polymers with diphosphonate have been extensively attracted.1. A new complex [Eu(1,10-phen)₂](NO₃)₃ was synthesized under the catalytic [ (iPrO)₂P(O)CH₂P(O)(iPrO)₂], and the crystal was characterized by IR, Element analysis and X-ray diffraction. In the reaction, [ (iPrO)₂P(O)CH₂P(O)(iPrO)₂] was not coordinated to the Europium atom, The function of the [ (iPrO)₂P(O)CH₂P(O)(iPrO)₂] was catalyst.2. In the basis study of Dy(OTf)₃, DyCl₃ and rare earth diphosphonate complex [Dy(OTf)₂L₂(H₂O)₂](OTf)(CH₃CN) (L=[ (iPrO)₂P(O)CH₂P(O)(iPrO)₂]) the catalytic effect in the reaction of Mannich, we studied 12 rare earth chlorides and their complexes with the ligands involving phosphoryl (P=O) group in this Mannich reaction.We found that when the diphosphonate(L) 1:1 coordinated with rare earth chloride, the corresponding catalysis capacity will be lower than the pure rare eatth chloride as catalyst, excepting are the complexes : CdCl₃, TmCl₃ with ligand L (1:1), when the complexe which CdCl₃ with ligand L (1:1) as catalyst, the formation of materials has not declined than the single catalyst CdCl₃. The overall trend is the catalystic efficency of the chlorides with L(1:2) between the pure chlorides and chlorides with L (1:1).3. A number of solid rare earth complexes with the compounds involving phosphoryl (P=O) group as the first ligand and the compounds involving nitrogen atom as auxiliary ligand have been synthesized. The compounds involving phosphoryl (P=O) group are tetraisopropylmethylenediphosphonate ((iPrO)₂P(O)CH₂P(O)(OiPr)₂), triphenylphosphine (Ph₃P=O) , bis(diphenylphosphino)methane (Ph₂P(O)CH₂P(O)Ph₂), bis(diphenylphosphino)ethane (Ph₂P(O)CH₂CH₂P(O)Ph₂), and 1,3-bis(diphenylphosphino) 1,3-(Ph₂P(O)(CH₂)₃P(O)Ph₂). The auxiliary ligands are phenanthroline(phen), o-phenylenediamine , ethanedioic acid, ₂-Amp, ₂-mercaptobenzothiazole(2-mbt), 2,2'-bipyridine(2,2'-bpy), imidazole(im), benzimidazole (benzim), pyrazine(pyz), quinoline(quin) and 4,4'-bipyridine(4,4'-bpy), etc.