Synthesis Of Novel Phosphine-containing β-diketiminato Rare-earth Metal Complexes And Their Application In Hydroaminoalkylation

This dissertation discusses the synthesis of a series of novel tridentate NNP alkyl(2-3)and aryloxide rare-earth complexes(4-5)and the cationic o-dimethylaminophenyl scandium complexes(12-13).All the complexes were characterized by elemental analysis,1D NMR and 2D NMR,while typical complexes are characterized by single crystal diffraction analysis.Further progress explored the reactivity of these rare-earth metal complexes in small molecule activation and C-H bond activation.1.A brand-new phosphine-containing β-diketiminato-ligand was synthesized for the first time.The ligand was prepared by multiple steps instead of traditional dehydration condensation method.Reaction of the ligand with rare-earth metal alkyl compounds generated the corresponding complexes(2-3).Treatment of 2 with equimolar of 2,6-diisopropylphenol afforded the monoalkyl/monoaryloxide scandium complex,while treating 2 with two equivalent of 2,6-diisopropylphenol gave the diaryloxide scandium complex as product.The activation reactivities of 4 and 5 towards small molecules such as H2、CO2、Ph CHO was studied.2.Using the synthesized alkyl scandium complex 2 and [Ph NHMe2][B(C6F5)4] as catalyst,tertiary arylamines could undergo catalytic reactions with alkenes to form the C(sp3)-H alkylation product.Reaction conditions were screened later.Under the optimized reaction condition,22 examples of C(sp3)-H alkylation products were obtained in high yields with good regioselectivities.Additionally,complex 12 was isolated and characterized,followed by catalytic and deuterium-labled studies.Experimental results showed that transformation of C(sp2)-H to C(sp3)-H took place in aniline substrate.This was also the first report that substituted N,N-dimethylaniline could react with unactivated alkenes in a C(sp3)-H hydroaminoalkylation reaction mode.