Date of Award

1995

Degree Type

Dissertation

Degree Name

Ph.D.

Department

Chemistry and Biochemistry

First Advisor

Loeb, Stephen J.,

Keywords

Chemistry, Inorganic.

Rights

CC BY-NC-ND 4.0

Abstract

The dissertation describes the incorporation of a stable organopalladium fragment into several macrocyclic structures, in which three of four palladium coordination sites are permanently occupied by an S$\sb2$C ligand "bracket". The remaining metal site is filled by a more labile donor, and is used for binding ancillary ligands (substrates) such as phosphines, o-aminopyridine, DNA nucleobases and hydrazine derivatives. Chapter 2 describes the synthesis, oxidative addition, and coordination chemistry of (Pt(TT(11) MC)) (BF$\sb4\rbrack$ (4), (PD(TT(11) MC)) (BF$\sb4\rbrack$, (8) and (Pd(pr-TOMB-1)) (BF$\sb4\rbrack$ (14), in which one donor (E = S,O) is displaced by stronger ancillary ligands, as confirmed by X-ray structural data as well as $\sp1$H and $\rm\sp{13}C\sp{1H}$ NMR spectroscopy. Chapter 3 describes the synthesis of several metalated macrocyclic receptors, (Pd(CH$\sb3$CN)(TOMB-0)) (BF$\sb4\rbrack$ (21), (Pd(CH$\sb3$CN)(TOMB-1)) (CF$\sb3$SO$\sb3\rbrack$, (23) (Pd(CH$\sb3$CN)(TOMB-3)) (BF$\sb4\rbrack$, (25) and (Pd(CH$\sb3$CN)(TOMB-5)) (BF$\sb4\rbrack$, (26), containing an easily displaced ancillary acetonitrile ligand and polyether arrays for first- and second-sphere interactions with substrates. The receptors were characterized by $\sp1$H NMR spectroscopy and X-ray crystallography. Chapter 4 describes competition experiments of 21, 23, and 25 for pyridine and o-aminopyridine in which it was found that an increase in the number of oxygen atoms increases selectivity for o-aminopyridine. In extraction experiments performed in acetonitrile with the DNA nucleobases, only 21 was found to extract adenine in any appreciable amount, and 25 exhibits molecular recognition for cytosine, over adenine and guanine. The nature of the first- and second-sphere interactions was determined by X-ray crystallography. Chapter 5 describes the optimization of simultaneous first- and second-sphere interactions using primary amines and hydrazine derivatives as substrates, with 25 and 26 as receptors. Receptor 25 was found to be selective for n-butylamine over N-methylbutylamine. Both receptors exhibit remarkable interactions with hydrazine derivatives, forming 4 point and 7 point interactions between the hydrazinium cation and 25 and 26 respectively, as determined by X-ray crystallography. Chapter 6 describes the development of a new receptor, incorporating a ferrocene moiety for additional characterization of receptor-substrate interactions. Metalation of the macrocycle proved to be difficult due to reduction of the palladium starting material by the ferrocene moiety.Dept. of Chemistry and Biochemistry. Paper copy at Leddy Library: Theses & Major Papers - Basement, West Bldg. / Call Number: Thesis1994 .K50. Source: Dissertation Abstracts International, Volume: 56-11, Section: B, page: 6107. Adviser: Stephen J. Loeb. Thesis (Ph.D.)--University of Windsor (Canada), 1995.

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