자료유형  

 학위논문

Control Number  

0016932827

International Standard Book Number  

9798379846312

Dewey Decimal Classification Number  

540

Main Entry-Personal Name  

Perales, Diana.

Publication, Distribution, etc. (Imprint  

[S.l.] : Purdue University., 2022

Publication, Distribution, etc. (Imprint  

Ann Arbor : ProQuest Dissertations & Theses, 2022

Physical Description  

1 online resource(203 p.)

General Note  

Source: Dissertations Abstracts International, Volume: 85-01, Section: B.

General Note  

Advisor: Bart, Suzanne C.

Dissertation Note  

Thesis (Ph.D.)--Purdue University, 2022.

Restrictions on Access Note  

This item must not be sold to any third party vendors.

Summary, Etc.  

요약While crucial advancements have been made in understanding transition metal−nitrogen interactions, the actinides have not been studied in such depth as their transition metal counterparts. Uranium has shown to catalyze the Haber−Bosch process to produce NH3 but more attention has turned to transition metals such as iron due to their low cost and accessibility. It is thought that transition metal imido species are essential intermediates to this process; therefore, it is critical to understand NH bond cleavage and formation on the metal. To study the potential that uranium has, it is important to bridge the knowledge gap of uranium with its transition metal counterparts and further understand NH bond cleavage and formation on the metal to make the suspected imido intermediate.Redox neutral methods have been popular and effective for synthesizing uranium imido complexes such as starting with a uranium(IV) amide and deprotonating it with a base to yield its respective uranium(IV) imido. It was of interest to understand if the bisTp* uranium(III) system would be amenable to a deprotonation pathway. To test this, the reactivity of Tp*2UBn with bulky 4-(2,6-di(pyridin-2-yl)pyridin-4-yl)benzenamine (terpy-aniline) and sterically smaller p-toluidine (ptol-aniline) was explored to first synthesize uranium(III) anilido species. Following successful synthesis, their reactivity is explored to yield respective uranium(IV) imido species by oxidative deprotonation.In addition to redox neutral methods, synthetic processes that rely on redox reactions at the uranium center have also been successful but are less common since the starting material must be a stable, low-valent uranium species. Our group has explored this method to make uranium(IV) imido species where the addition of 1 equivalent of organic azide to trivalent Tp*2UBn or one equivalent of organic azide and potassium graphite to Tp*2UI results in the formation of uranium(IV) imido species. The downside to this is azides are explosive and their synthesis could inhibit synthesis of diverse complexes. A redox method that eliminated usage of explosive azides is of interest so the reactivity of hydrogen atom transfer (HAT) reagents, Gomberg's dimer or the 2,4,6-tritBu-phenoxy radical (·OMes*), with uranium(III) anilido complexes of varying steric bulk and electronic profile was explored. Conversion to their respective uranium(IV) imido species was achieved and this method was also explored with uranium(III) amides smaller than a phenyl since their respective azide are too dangerous to synthesizeFollowing isolation of uranium(III) anilido complexes and exploring reactivity it was of interest to understand how they compare to phosphorus analogues and how reactivity and interactions might be similar. Reactivity of Tp*2UBn with phosphines of various steric bulk and electronic profile allowed for the isolation of uranium(III) phosphido complexes and their reactivity showed to be different than previously explored uranium(III) anilido counterparts. The electronic differences of the pnictogens were also observed in the crystal structures.With the differences in reactivity and electronic effects between the nitrogen and phosphorous complexes having been observed, our curiosity expanded to explore more uraniumpnictogen interactions. Therefore, synthesis of bis-substituted arsine and bis-substituted phosphine ligands were conducted for reactivity with Tp*2UBn. Preliminary data reveals these bonds are more unstable and reactive relative to uranium(III) anilido species, likely due to the electronic mismatch between oxophilic uranium and soft pnictogens.

Subject Added Entry-Topical Term  

Crystal structure.

Subject Added Entry-Topical Term  

Hydrocarbons.

Subject Added Entry-Topical Term  

Deportation.

Subject Added Entry-Topical Term  

Oxidation.

Subject Added Entry-Topical Term  

Uranium.

Subject Added Entry-Topical Term  

Single crystals.

Subject Added Entry-Topical Term  

Carbon.

Subject Added Entry-Topical Term  

Solvents.

Subject Added Entry-Topical Term  

Hydrogen.

Subject Added Entry-Topical Term  

Azide.

Subject Added Entry-Topical Term  

Potassium.

Subject Added Entry-Topical Term  

Molecular structure.

Subject Added Entry-Topical Term  

Radiation.

Subject Added Entry-Topical Term  

Crystallography.

Subject Added Entry-Topical Term  

Nitrogen.

Subject Added Entry-Topical Term  

Inorganic chemistry.

Subject Added Entry-Topical Term  

Nuclear chemistry.

Added Entry-Corporate Name  

Purdue University.

Host Item Entry  

Dissertations Abstracts International. 85-01B.

Host Item Entry  

Dissertation Abstract International

Electronic Location and Access  

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Control Number  

joongbu:643415