Title

A Foundational Study of a New Synthestic Method of Metal Carbonyl Clusters

Publication Date

8-2019

Date of Final Oral Examination (Defense)

5-8-2019

Type of Culminating Activity

Thesis

Degree Title

Master of Science in Chemistry

Department

Chemistry

Major Advisor

Adam C. Colson, Ph.D.

Advisor

Eric C. Brown, Ph.D.

Advisor

Michael P. Callahan, Ph.D.

Abstract

“Traditional” Metal Carbonyl Clusters (MCCs) contain a framework of multiple metal atoms bound together through formal metal-metal (M-M) bonds. Current methods of synthesis result in different cluster sizes and lack a method to control growth. This project proposes a new method of MCC synthesis to build larger structures utilizing secondary non-covalent interactions to develop “non-traditional” MCCs. The N,N’-diarylurea moiety is a strong hydrogen bond donor/acceptor that can induce self-assembly into larger secondary structures. The union of metal carbonyl and urea chemistry provides a potential method of “non-traditional” MCC synthesis. This proof of concept experiment will elucidate foundational information such as: reduction-oxidation potentials, chemical organization, chemical structure, and binding constants. The x-ray crystal structures detail a nearly planar molecular organization and refute the formation of urea ribbons due to a stabilizing intramolecular hydrogen bond interaction. Stabilizing π-π stacking and a urea-π stacking interactions were observed as a result of the planar orientation. A titration study confirms the strong anion binding capability of the metal carbonyl appended urea moiety and confirms anion binding as a possible method of coordinating multiple units together to build “non-traditional” MCCs. The π-π interactions and urea-π interactions were observed as the largest contributor to the molecular structure and as a result, the appended group 6 metal centers are separated by distances between 6.00 Å and 8.00 Å. The close contact between metal nuclei has the potential to allow for electrochemical communication albeit not with these compounds. The characterization and synthesis of 1,3-bis(p-isocyanophenyl)urea and its group 6 metal containing derivatives provided sufficient data to lay a solid foundation for continuing research.

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