Doctor of Philosophy
Professor Paul J. Ragogna
Main group chemistry has advanced from studying fundamental curiosities, including low oxidation state, low-valent, p-block elements to tailoring these unique, reactive species for specific functional applications. This thesis examines the structure, bonding and reactivity of select group 13, 14 and 15 elements supported by N,N'-chelating ligands decorated with either thiophene, benzo[1,2-b:5,6-b']dithiophene or bis(2,5-dimethylthienyl)ethene substituents and allowing for subsequent reactivity and photophysical properties to be determined.
The synthesis of a new diamino ligand containing a thiophene ring in the backbone was used to support a 7-membered phosphenium cation. The 1:1 stoichiometric reaction between the amine:chlorophosphine was dependant on the substitution at nitrogen. A 1:1 stoichiometric reaction between PCl3 and diamine (R = 2,4,6-trimethyphenyl), yielded the acyclic bis(aminodichlorophosphine), while with diisopropylphenyl groups on nitrogen both the 1:1 cyclic aminochlorophosphine and 1:2 acyclic bis(aminodichlorophosphine) were observed in a 4:1 ratio. To amend the poor selectivity, a new diamine was designed with benzo[1,2-b:5,6-b']dithiophene in the backbone as this ligand generates a rigid five-membered ring upon coordination to main group elements. The detailed synthesis of this ligand and its ability to support pnictenium cations (Pn = P, As and Sb) and their metal complexes were prepared, along with a discussion of spectroscopic properties. The synthesis of an N-heterocyclic carbene (NHC) with the benzo[1,2-b:5,6-b']dithiophene in the backbone, silver(I) transfer reagent and the BPh3 adduct were also synthesized. The donor strength of the NHC was measured from the carbonyl IR stretching frequencies of the isolated NHC-Rh(CO)2Cl complex along with the resulting photophysical properties.
The synthesis of a versatile diimine ligand containing adjacent 2,5-dimethyl(thienyl) rings in the backbone and its coordination to main group atoms was also achieved. This diazabutadiene acts as a precursor to a novel photochromic ligand that has been used to coordinate to both boron and phosphorus elements, along with the synthesis of a phosphorane side chain functionalized polymer. A study of the resulting photochromic properties of these compounds was completed and the following was observed: (i) The UV-visible absorption spectra of the ring closed isomer was dependent of the element present in the N,N'-chelating pocket; and (ii) incorporating the dithienylethene into a side functionalized phosphorane polymer greatly increased the ring closed/open reversibility and decreased the formation of by-products.
Price, Jacquelyn T., "Novel Thiophene Supported N,N'-Chelating Ligands and Their Main Group Compounds" (2013). Electronic Thesis and Dissertation Repository. 1304.