Date of Award

9-26-2000

Document Type

Dissertation

Degree Name

Doctor of Philosophy (PhD)

Department

Chemistry

First Advisor

Lothar Stahl

Abstract

Synthesis and characterization of several bis(aminoaryl)cyclodiphosph(III)azanes were described. NMR spectroscopy, mainly 13C and 31 P NMR, was used to determine whether these bis(amino) compounds existed in cis or trans configuration. From this information, it was determined which ligands were potential chelates. Treatment of the cis-bis(aminoaryl)cyclodiphosph(III)azanes with TiCl4 and a base yielded pseudotetrahedral 14-electron complexes that can be used in olefin polymerization processes. Lithiation of these ligands yielded the dilithium salts, which were excellent starting materials for metathesis reactions. Upon treatment of ZrCl4 and HfCl4 with the dilithio salts, these bis(arylamido)cyclodiphosph(III)azanes were found to coordinate two ligands forming pseudooctahedral complexes that find no potential use as catalysts. Due to deactivation of the catalytic process by the lone-pair of electrons on these bis(amido)cyclodiphosph(III)azanes metal complexes, these ligands along with cis-(NtBuP)2(NH tBu)2 were oxidized with aryl azides, forming bis(amino)-bis(imino)-cyclodiphosph(V)azanes. These dual-functional compounds had potential to coordinate two metals. Upon treatment with TiCl4 and a base, the titanium was inserted into the ligand forming a complex containing a heteroallylic N-P-N chelating unit. The bis(amino) and bis(amino)-bis(imino) ligands and their respective metal complexes were spectroscopically characterized using NMR techniques and structurally characterized by single crystal X-ray analysis.

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