Direct Halogenation of TpRu(diene)Cl Preceding Ligand Exchange Reactions and Assessment of the Halogenated Complexes via Oxidation Potentials and Catalysis

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dc.contributor.advisorMay, Jeremy A.
dc.contributor.committeeMemberDaugulis, Olafs
dc.contributor.committeeMemberDo, Loi H.
dc.contributor.committeeMemberBrgoch, Jakoah
dc.contributor.committeeMemberFaler, Catherine A.
dc.creatorHattori, Hiroyuki 1988-
dc.date.accessioned2020-01-04T03:04:57Z
dc.date.createdMay 2019
dc.date.issued2019-05
dc.date.submittedMay 2019
dc.date.updated2020-01-04T03:04:57Z
dc.description.abstractThe focus of this dissertation centers on the direct on-metal halogenation of trispyrazoyl borate ligand (Tp) in TpRu(diene)Cl. The first chapter begins with the preparation of TpRu(diene)Cl complexes and assessment of their stability under different conditions. TpRu(diene)Cl complexes were halogenated in one step using sulfuryl chloride, NBS, and iodine in the presence of mCPBA and H2O and then also functionalized through Sonogashira coupling reactions. Through this methodology, TpClRu(diene)Cl, TpBrRu(diene)Cl, TpIRu(nbd)Cl, and, TpC≡CHRu(nbd)Cl were synthesized via an unusual strategy. The next chapter encompasses the syntheses of simple di-phosphine complexes (dppm to dppb) and mono-phosphine complexes from the TpXRu(diene)Cl obtained in the previous chapter. By synthesizing the di-phosphine complexes of different P-P linker lengths, changes to the chemical properties of the complexes were investigated. Mono-phosphine complexes TpXPPh3Cl2 were synthesized via a reported reaction reported for TpRuPPh3Cl2, and other mono-phosphine complexes TpXRuPPh3(MeCN)Cl were derived from the counterpart TpXRuPPh3Cl2 with newly devised reaction conditions. These phosphine complexes, in addition to the new diene complexes, were analyzed with cyclic voltammetry. Lastly, the synthesized complexes were subject to evaluation of their catalysis. Two investigatory reactions used were (1) propargylic substitution and furan synthesis from epoxy alkynes. Propargylic substitution reactions gave a mixture of copious compounds from which the product was not isolated. Furan synthesis gave the expected furan, but in an unexpectedly low yield. Increasing the catalyst loading barely enabled a comparison between differently halogenated complexes. In TpXRuPPh3Cl2 catalysis, TpClRuPPh3Cl2 gave a slightly higher yield (17%) than the analogues (14%). On the other hand, TpRuPPh3(MeCN)Cl (26%) and TpIRuPPh3(MeCN)Cl (28%) gave slightly higher yield than the chlorinated (23%) and brominated (22%) complex.
dc.description.departmentChemistry, Department of
dc.format.digitalOriginborn digital
dc.format.mimetypeapplication/pdf
dc.identifier.citationPortions of this document appear in: Hattori, Hiroyuki, Dong Hyun Koo, and Jeremy A. May. "Direct Chlorination of Trispyrazolyl Borate Ligands in Tp-Ruthenium Complexes." Organometallics 36, no. 24 (2017): 4707-4712.
dc.identifier.urihttps://hdl.handle.net/10657/5756
dc.language.isoeng
dc.rightsThe author of this work is the copyright owner. UH Libraries and the Texas Digital Library have their permission to store and provide access to this work. UH Libraries has secured permission to reproduce any and all previously published materials contained in the work. Further transmission, reproduction, or presentation of this work is prohibited except with permission of the author(s).
dc.subjectDirect Halogenation
dc.subjectTpX ligand
dc.titleDirect Halogenation of TpRu(diene)Cl Preceding Ligand Exchange Reactions and Assessment of the Halogenated Complexes via Oxidation Potentials and Catalysis
dc.type.dcmiText
dc.type.genreThesis
local.embargo.lift2021-05-01
local.embargo.terms2021-05-01
thesis.degree.collegeCollege of Natural Sciences and Mathematics
thesis.degree.departmentChemistry, Department of
thesis.degree.disciplineChemistry
thesis.degree.grantorUniversity of Houston
thesis.degree.levelDoctoral
thesis.degree.nameDoctor of Philosophy

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