Title

Syntheses and Characterizations of Bis(Diazasilaphosphetidine)Amine, P, N-2-Phosphinoaminopyridine and Phosphaacetylferrocenyl Ligands, and Some of Their Metal Complexes

Date of Award

8-1-2007

Document Type

Dissertation

Degree Name

Doctor of Philosophy (PhD)

Department

Chemistry

Abstract

Symmetric bis(diazasilaphosphetidine)amine chelating ligands of the general formula {Me2Si(p-Nt-Bu)P}2N(Ar) where Ar = C6H4(/?-OMe), C6H4(/7-Me) and C6F5, and asymmetric bis(phosphine)amine ligands have been synthesized by treatment of chlorophosphines or chlorophosphite with the corresponding lithium amides. The asymmetric ligand Me2Si(p-Nt-Bu)2P(=NPh)PPh2 served either as a P,P or a P,N chelate depending on the metal ion and the reaction conditions employed. R./V-2-phosphinoaminopyridine ligands such as [{2-(/-Bu2PNH)C5NH4}LiCl]*C4HgO and [{2-(Me2Si(p-Nf-Bu)2PNH)C5NH4}LiCl]*C4HgO with different substituents at phosphorus have also been synthesized. Numerous molybdenumtetracarbonyl, nickel and palladium complexes of these ligands have been synthesized. The synthesized compounds have been characterized by elemental analysis, melting point, NMR and 1R spectroscopic techniques, and by single crystal X-ray diffraction technique. Acetylferrocenylphosphines have been synthesized and oxidized with S or Se to give ligands that have potential use in the synthesis of late-transition metal neutral catalysts. The zinc complex of acetylferrocenylphosphine, [{FcAcP(=S)Ph2}ZnEt]2, was synthesized by treating the corresponding ligand with diethylzinc.

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