Cancer is a disease that affects millions around the globe. Treatments such as radiation and chemotherapy are often used to treat cancerous tumors, but are not 100% effective in curing the patient. Alternatively, some research groups have proposed the use of metallointercalators, metal complexes consisting of a rhodium, ruthenium, or iridium metal center with bidentate supporting ligands such as bipyridine and phenanthroline, or tridentate ligands such as terpyridine. The complexes also contain a bidentate intercalating group such as dipyridophenazine. These complexes possess the ability to directly bind to DNA through intercalation between the stacks of DNA base pairs, giving them the potential to be used as probes to analyze and identify chemically damaged DNA. The ultimate goal would be to design molecules that could detect damaged DNA at the molecular level and allow treatment before tumors could develop. Our objective is to design and synthesize novel metallointercalator complexes of rhenium, and to examine their physical and spectroscopic properties. Specifically, we are attempting to prepare [Re(Py2NO)(dppz)L]3+, where L = H2O or NH3. (Py2NO = 4,4-dimethyl-2,2-di(2-pyridyl)oxazolidine; dpk-OEt = (py)2C(O)OCH2CH3; dppz = dipyridophenazine). Reaction of TBA2[Re2Cl8] with the nitroxide ligand Py2NO in acetonitrile produces a red/brown compound proposed to be Re(Py2NO)Cl3. Isolation and purification of this compound has proven to be a challenge. NMR studies indicate the compound is present as an intractable mixture. When the same reaction is performed in ethanol, the blue complex ReO(dpk-OEt)Cl2 is obtained. The same compound can be isolated in good yield by direct reaction of two equivalents of di-2-pyridyl ketone with TBA2[Re2Cl8]. The blue complex has been reacted with two equivalents of Ag+ followed by the addition of dppz to produce a brown solid believed to be the metallointercalator [ReO(dpk-OEt)dppz]2+. Details of the synthesis along with IR, NMR, and UV/Vis spectral characterization of these compounds are described.
Dr. Steven Haefner, Thesis Advisor
Dr. Thayaparan Paramanathan, Committee Member
Dr. Samer Lone, Committee Member
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Original document was submitted as an Honors Program requirement. Copyright is held by the author.
Schwartz, Eli. (2019). Synthesis of Novel ReIII and ReV Metallointercalator Complexes for Use as DNA Damage Probes. In BSU Honors Program Theses and Projects. Item 397. Available at: https://vc.bridgew.edu/honors_proj/397
Copyright © 2019 Eli Schwartz