Date of Award
Chemistry and Biochemistry
Stephan, D. W.,
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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 2,6-positions of the N-phenyl ring (compounds 44 and 45), oxidative addition of CH2Cl2 was not observed. The reaction of Group X transition metals with phosphinimine ligands was also explored. Attempts to coordinate [Li(o-C6H 4PPh2NR)]2·Et2O (R = SiMe 3 61 and tBu 62) to Group X transition metals proved to be unsuccessful due to steric congestion. However, transmetallation did occur when less bulky phosphinimine ligands were used, such as, [Li(o-C6H4PPh2NR)] 2·Et2O (R = Ph 63 and 3,5-C6H 3(CH3)2 66). The Group X phosphinimine complexes described herein, [Ni(o-C6H4PPh 2NR)2] (R = Ph 67 and 3,5-C6H 3(CH3)2 68) and [Pd(o-C 6H4PPh2NPh)2] 69, were bis-ligand type complexes.Dept. of Chemistry and Biochemistry. Paper copy at Leddy Library: Theses & Major Papers - Basement, West Bldg. / Call Number: Thesis2003 .C46. Source: Masters Abstracts International, Volume: 42-02, page: 0594. Adviser: D. W. Stephan. Thesis (M.Sc.)--University of Windsor (Canada), 2003.
Chan, Katie Tak-Kwan., "Metallated group IX and group X phosphinimine complexes." (2003). Electronic Theses and Dissertations. 2714.