Author

Ingo Schranz

Date of Award

9-12-2008

Document Type

Dissertation

Degree Name

Doctor of Philosophy (PhD)

Department

Biology

First Advisor

Stahl, Lothar

Abstract

Syntheses, spectroscopic and X-ray structural characterizations of chelating ligands containing diazasilaphosphetidine rings are described. The diamines orthophenylenediamine, 1,2-trans- diaminocyclohexane, and hexamethylenediamine were treated with two equivalents of [Me2Si(p-NtBu)2PCl], 14, producing 1,2- [Me2Si(tBuN)2PN(H)]2C6H4, 95, l,2-rraw-[Me2Si(‘BuN)2PN(H)]2C6Hi0, 105, and 1,6- [Me2Si(tBuN)2PN(H)]2(CH2)6, 108, respectively. In addition, 2,6-diisopropylaniline were monolithiated, and treated with [Me2Si(p-NtBu)2PCl], producing Me2Si(BuN)2PN(H)- 2,6-'Pr2Ph, 112. These phosphorus (III) containing molecules were oxidized with cumene hydroperoxide, elemental sulfur, and p-tolyl azide, producing P=E bonds where E = O, S, N-jp-tolyl. The resulting amino(imino)- and amino(chalcageno)phosphoranes were deprotonated producing negatively charged (N-E) ligands which can chelate zirconium (IV), and nickel (II). These transition-metal complexes may be active precatalysts for aolefin polymerization.

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