­^¤åºK­n Chapter 1 A new chelating N,N ligand family incorporating an anilido-phosphinimine donor set has been designed. The ligand1-(NHAr)-2-(PPh2=NAr¡¦)C6H4(iPr[NN]DippH: Ar = 2,6-iPr2-C6H3, Ar¡¦ = 2,6-iPr2-C6H3; iPr [NN]MesH: Ar = 2,6-iPr2-C6H3, Ar¡¦ = 2, 4, 6-Me3C6H2; Me[NN]MesH: 2,6-Me2-C6H3, Ar¡¦ = 2, 4, 6-Me3C6H2) were synthesized via a route of reacting amido phosphine ligands with aryl azides. We observed different behaviors of adding n-BuLi in different solvents. In 31P NMR, we found the changed of chemical shift upon the different Ar¡¦ substituents. When substituent on Nphosphinimine was Dipp, there are larger chemical shift change. Addition of [NN]H to ZnMe2 or ZnEt2 in toluene or Et2O at -35oC generated the monomeric, three-coodinate [NN]ZnR (R = Me, Et)(schem 1), while the metathesis reaction of Zn(OAc)2 with iPr[NN]DippLi(Et2O) in THF at -35oC produced iPr[NN]DippZnOAc. But in the same condition, we made the iPr[NP] iPrLi(DME) produced homoleptic {iPr[NP] iPr}2Zn. All of the complexes were characterized by multinuclear NMR spectroscopy or X-ray crystallography. We used [NN]ZnR catalyzed ring-opening polymerization of £`-Caprolactone . The results of catalysis had good yields in 90 to 100% and narrow PDI around 1.5. But they are not a living polymerization catalysis. Chapter 2 We use {[NP]NiCl}2 catalyzed Kumada reactions of alkyl halide or aryl halide with Grignard reagent. In the result, Used {iPr[NP]iPr}2NiCl catalyzed aryl halide with Grignard reagent is better than other {[NP]}2NiCl, but not good catalyzed alkyl halide with Grignard reagent. We do kinetic studies of benzene C-H bond activation by nickel complexes of amido phosphine ligand. By the result, We can defind the benzene C-H bond activation was association rection.

1. Benzene C-H Activation by Nickel(II) and Platinum(II) Complexes of Chelating Diarylamido Phosphine Ligands We have demonstrated an efficient intermolecular benzene C-H activation process mediated by Ni(II) complexes of ([Me-NP-iPr]Ni(L)(R)(L = Pyridine, 2,4-Lutidine, PMe3) and [iPr-NP-Ph]Ni(PMe3)(R) (R = Me, CH2SiMe3). When Lewis base is PMe3 or substituent is CH2SiMe3 more reactivity is observed. The amido diphosphine complexes [iPr-PNP]PtOTf effectively activate the benzene C-H bond in the presence of an appropriate Lewis base(NEt3 or DABCO). 2. Metal Complexes of Amido Phosphine Ligand Bearing Unsymmetric Donor Atom: Syntheses, Structures and Reactivities A series of [Ph-PNN]Ni(II)R (R = Me, Et, Ph, CH2Ph) complexes containing £]-hydrogen atoms have been prepared and characterizated. We have demonstrated an efficient intermolecular arene C-H activation process mediated by Ni(II) complexes of [Ph-PNN]NiEt at elevated temperature. A series of nickel(II) complexes featuring an unsupported, covalently bound p-donor ligand including anilide, phenolate, thiophenolate and tert-butoxide derivatives have been prepared and characterizated. Novel unsymmetric tridentate ligands (H[R-PNO], R = iPr, Ph) have been prepared and characterized. The reaction of [iPr-PNO]NiCl with Na/Hg in thf or ether at room temperature induced C-O bond activation followed by the generation of {[iPr-PNO]Ni}{[iPr-PNO*]NiMe}. 3. Amido Diphosphine Complexes of Cobalt: Syntheses, Structures and Reactivities A series of paramagnetic divalent cobalt complexes ([R-PNP]CoCl, R = iPr, Cy) supported by tridentate diarylamido phosphine ligands have been prepared and characterized. The diamagnetic monovalent cobalt-dinitrogen complexes ([R-PNP]Co(N2), R = iPr, Cy) are accessible from the reaction of [R-PNP]CoCl with LiHBEt3 in THF solution. The dinitrogen complex [Cy-PNP]Co(N2) reacts in THF with terminal alkynes, HC¡ÝCR, yielding vinylidene complexes ([Cy-PNP]Co=C=C(H)(R), R = Ph, SiMe3). The dinitrogen complex [Cy-PNP]Co(N2) and {[iPr-PNP]Co}2(£g-N2) reacts in THF with diphenylacetylene (PhC¡ÝCPh) yielding p complexes ([R-PNP]Co(h2-PhC¡ÝCPh), R = iPr, Cy). 4. Fluorinated Mono- and Diarylamido Complexes of Lithium and Group 4 Metals The synthesis of bis-ligand Group 4 metal complexes ([iPrAr-NF]2MCl2, M= Zr, Hf) are utilizing [iPrAr-NF]Li and MCl4(THF)2. The alkylation of [iPrAr-NF]2MCl2 with RMgCl (R= Me, iBu, PhCH2, Me3SiCH2) produced a series of group 4 metal complexes ([iPrAr-NF]2MR2, M= Zr, Hf) which are catalyst precursors for olefin polymerization. Deprotonation of H[iPr-NF] and H[Cy-NF] with n-BuLi in ethereal solutions at -35 ¢XC produced the lithium complexes {[iPr-NF]Li(solv)}2 (solv = THF, Et2O) and {[Cy-NF]Li(Et2O)}2, respectively. The metathetical reaction of [iPr-NF]Li(Et2O) with 1/3 equiv TiCl4(THF)2 in toluene solution produced the trianilide titanium complex [iPr-NF]3TiCl. A series of novel fluorinated bidentate (H[Mes-NP-RF], R = iPr, Ph) and tridentate ligands (H2[Mes-NPNF]) have been prepared and characterizated.