dc.contributor.advisor | Neilson, Robert H. | |
dc.contributor.author | Samuel, Remy C. | en_US |
dc.date.accessioned | 2019-10-11T15:10:03Z | |
dc.date.available | 2019-10-11T15:10:03Z | |
dc.date.created | 1992 | en_US |
dc.date.issued | 1992 | en_US |
dc.identifier | aleph-590086 | en_US |
dc.identifier | Microfilm Diss. 592. | en_US |
dc.identifier.uri | https://repository.tcu.edu/handle/116099117/31808 | |
dc.description.abstract | N-Silylphosphoranimines are the small molecule precursors to poly(alkyl/arylphosphazenes), (R$\sb2$P = N) $\sb{\rm n}$. Most of these N-silylphosphoranimines are obtained via suitably constructed (silyamino)phosphines. The trifluoroethoxy and phenoxy derivatives of the N-silylphosphoranimines containing the Me$\sb3$Si moiety have been reported earlier and are very good precursors to poly(alkyl/arylphosphazenes).(DIAGRAM, TABLE OR GRAPHIC OMITTED...PLEASE SEE DAI) The effect of having bulky silyl groups on the nitrogen has not been studied previously. Therefore, the (silylamino)phosphines and N-silylphosphoranimines containing t-BuR$\sb2$Si (R = Me, Ph) and Et$\sb3$Si were synthesized. The main reason for preparing derivatives with the bulky t-BuPh$\sb2$Si moiety on nitrogen, was the possibility that this moiety would impart crystallinity to the compounds. As a result of this steric bulk a few of these compounds tended to crystallize and were characterized by X-ray crystallography. Three molecules could be considered as structural models for the precursor chemistry involved. A notable point is that these acyclic compounds crystallized without the assistance of metal complexation or cyclization reactions.(DIAGRAM, TABLE OR GRAPHIC OMITTED...PLEASE SEE DAI) Condensation reactions were also carried out on some of these (silylamino)phosphines and N-silylphosphoranimines, so as to examine the effect of the presence of the above mentioned bulky silyl substituents. A number of copolymerization reactions were also carried out with the intention of end-capping the polymer formed using a blocking group. These reactions were conducted using the conventional sealed-tube technique as well as a recently developed catalyzed route. On thermolysis, the P-phenylchlorophosphine containing the bulky t-BuPh$\sb2$Si moiety decomposed to give a unique P(III)-P(V) containing P$\sb2$N$\sb2$ ring system. X-ray analysis of this compound was also obtained.(DIAGRAM, TABLE OR GRAPHIC OMITTED...PLEASE SEE DAI) | |
dc.format.extent | viii, 150 leaves : illustrations | en_US |
dc.format.medium | Format: Print | en_US |
dc.language.iso | eng | en_US |
dc.relation.ispartof | Texas Christian University dissertation | en_US |
dc.relation.ispartof | AS38.S268 | en_US |
dc.subject.lcsh | Polyphosphazenes | en_US |
dc.subject.lcsh | Phosphorus compounds | en_US |
dc.title | Synthesis, characterization, and condensation reactions of some new (silylamino)phosphines and N-silylphosphoranimines | en_US |
dc.type | Text | en_US |
etd.degree.department | Department of Chemistry | |
etd.degree.level | Doctoral | |
local.college | College of Science and Engineering | |
local.department | Chemistry and Biochemistry | |
local.academicunit | Department of Chemistry | |
dc.type.genre | Dissertation | |
local.subjectarea | Chemistry and Biochemistry | |
dc.identifier.callnumber | Main Stacks: AS38 .S268 (Regular Loan) | |
dc.identifier.callnumber | Special Collections: AS38 .S268 (Non-Circulating) | |
etd.degree.name | Doctor of Philosophy | |
etd.degree.grantor | Texas Christian University | |