Synthesis And Reaction Properties Of Rare Earth Metal Phosphonium Complexes Based On Polydentate Nitrogen Ligands

At present,the research of rare-earth metal phosphinidene complexes is limited to bridged type and not comprehensive,and the terminal one has not yet been successfully stability and separation.The Exploration of synthesis and reactivities of the rare-earth metal phosphinidene complexes is useful for the expansion of the rare-earth complexes system.It can also helps people deeply comprehend the rules of the hard and soft acid-base.The dissertation mainly focused on the reactivities of rare-earth metal bridged phosphinidene complexes and the attempting to the synthesis of rare-earth metal terminal phosphinidene complexes.1.The scandium bridged phosphinidene complex 1[LSc(?-PAr)]2(L =(MeC(NDIPP)-CHC(Me)(NCH2CH2N('Pr)2)),DIPP = 2,6-('Pr)2C6H3;Ar = 2,6-Me2C6H3))has novel and interesting reactivities:? Reactions of scandium bridged phosphinidene complex 1 with catecholborane,pinacolborane,and 9-borabicyclo[3.3.1]nonane(9-BBN)show different reaction patterns.Depending on the substrate,B-O or B-H bond cleavage was observed.Although B(H)-O bond is stronger than B(O)-H bond,the reactions with pinacolborane and catecholborane give the B-O bond cleavage products-binuclear scandium pinacolate and binuclear scandium catecholate.? The complex 1 undergoes addition reactions with'Pr2NCN'Pr2 to generate unsymmetrical dual-core scandium complexes.? Complexes 1 reacts with diphenyl disulfide to give the scandium bridged sulfur complex[L(PhS)Sc(?-SPh)]2(L =(MeC(NDIPP)CHC(Me)(NCH2CH2N('Pr)2)),DIPP = 2,6-('Pr)2C6-H3).All the five generated complexes were characterized by single crystal X-ray diffraction.? Also explores the reaction of the complexes 1 react with alkyne.According to the 1H and 31P NMR,complexes 1 reacts with 1-hexyne to generate scandium alkynyl complexes and scandium dialkynyl complexes.But the products have not been characterized by X-ray single crystal diffraction.2.Attempting to the synthesis of rare-earth metal terminal phosphinidene complexe.Designed and synthesized phosphine ligand H[P]2 o-(o-NMe2C6H4)C6H4PH2 which with side chain coordination group,and phosphine hydrogen potassium K[P]2 o-(o-NMe2C6H4)-C6H4P(H)K.Try to synthesis of rare-earth metal terminal phosphinidene complexe by salt-alkyl eliminate path.Choose tridentate nitrogen ligand HL2(MeC(NDIPP)CHC(Me)(NCH2CH2N(Me)2))and bidentate nitrogen ligand HL'(MeC(NDIPP)CHC(Me)(NDIPP))respectively coordinated with rare-earth metal ions Sc3+ to gave scandium dichloride and scandium methyl chloride.Then,Scandium dichloride and Scandium methyl chloride respectively react with K[P]2.1H and 31P NMR show that based on didentate nitrogen ligand scandium methylchloride reacting with K[P]2 generated scandium methylphosphonic complex by elimination reaction,the others occur with ligands redistribution.The scandium phosphonic complex has not yet been separated successfully.This paper shows that 1 has interesting reavtivities;It will take time to successfully separate rare-earth metal terminal phosphinidene complexes.