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Syntheses And Applications Of Group Vi And Viii-X Heterocyclic-Phosphinimine Complexes., Liam P. Spencer
Syntheses And Applications Of Group Vi And Viii-X Heterocyclic-Phosphinimine Complexes., Liam P. Spencer
Electronic Theses and Dissertations
A class of phosphinimine-based group VI and VIII-X late transition metal (LTM) complexes has been synthesized and evaluated for olefin polymerisation activity. The phosphinimine ligand has been designed to incorporate an imine moiety; a functional group which has been successfully applied in very active LTM olefin catalytic systems. Heterocycles, such as pyridine and imidazole are used to accomplish the integration of an imine group into the ligand. Phosphines employing the heterocyclic group are oxidized by phenyl azides in excellent yields to form phosphinimine ligands. These phosphinimine ligands react with several LTM's, the complexes of which are identified by single crystal …
Group 8-10 Complexes Of Pyridyl-Phosphinimines And Chiral Bis-Diiminophosphoranes., Ramadan. Altwer
Group 8-10 Complexes Of Pyridyl-Phosphinimines And Chiral Bis-Diiminophosphoranes., Ramadan. Altwer
Electronic Theses and Dissertations
A group of exocyclic pyridyl-phosphinimine ligands have been prepared in excellent yields by oxidizing trip henylphosphine with 2-azidomethylpyridines. These ligands reacted with group 8--10 transition metals to form various late transition metal complexes (e.g. [Ph3P=NCH2(2-Py)]NiBr 2 36) which have been characterized and evaluated for olefin polymerization activity. We found that these complexes are not active for ethylene polymerization or oligomerization. In a similar sense, nickel complexes 55 and 56 were synthesized by the reaction of nickel dihalide with a chiral bis-diiminophosphorane ligands. The corresponding ligand was prepared by deprotonation of R-2,2' -diamino-1,1'-binaphthalenetriphenyldibromide by a strong base. The complexes were seemed …
Group Iv Phosphinimide Complexes In Catalysis., Emily Hollink
Group Iv Phosphinimide Complexes In Catalysis., Emily Hollink
Electronic Theses and Dissertations
Significant progress has been made in various aspects of the chemistry of Group IV phosphinimide complexes, particularly in their use as highly active catalysts for olefin polymerization upon activation by an appropriate Lewis acid. Advances in synthetic methods have provided routes for the preparation of phosphinimide amide inorganic and organometallic products via metathesis or protonation methods. Testing of TiCp(NPtBu 3)X2 (X = Cl, Me, NMe2) as hydroamination catalysts has shown that these complexes are inactive for this purpose under the conditions employed. In addition, numerous synthetic endeavours have revealed that the titanium phosphinimide complexes are reluctant to form isolable imide …
Metallated Group Ix And Group X Phosphinimine Complexes., Katie Tak-Kwan. Chan
Metallated Group Ix And Group X Phosphinimine Complexes., Katie Tak-Kwan. Chan
Electronic Theses and Dissertations
The focus of this research has been the preparation of late transition metal phosphinimine complexes. The thesis herein describes the synthesis of a series of monomeric Group IX phosphinimine complexes. [RhCOD(o-C 6H4PPh2NR)] (R = 2,6-C6H3(CH 3)2 44, 2,6-C6H3 iPr2 45, 3,5-C6H3(CH 3)2 46 and Ph 47) were prepared via salt metathesis under mild conditions. The analogous complexes [Rh( o-C6H4PPh2NPh)(Ph2PCH 2CH2PPh2)] 52 and [IrCOD( o-C6H4PPh2NPh)] 53 were also readily prepared by similar methods. Reactivity studies were performed on these complexes. Unexpectedly, complexes 46, 47, 52 and 53 underwent oxidative addition of methylene chloride. However, when steric bulk was introduced on the …