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dc.contributor.advisorNeilson, Robert H.
dc.contributor.authorSamuel, Remy C.en_US
dc.date.accessioned2019-10-11T15:10:03Z
dc.date.available2019-10-11T15:10:03Z
dc.date.created1992en_US
dc.date.issued1992en_US
dc.identifieraleph-590086en_US
dc.identifierMicrofilm Diss. 592.en_US
dc.identifier.urihttps://repository.tcu.edu/handle/116099117/31808
dc.description.abstractN-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)en_US
dc.format.extentviii, 150 leaves : illustrationsen_US
dc.format.mediumFormat: Printen_US
dc.language.isoengen_US
dc.relation.ispartofTexas Christian University dissertationen_US
dc.relation.ispartofAS38.S268en_US
dc.subject.lcshPolyphosphazenesen_US
dc.subject.lcshPhosphorus compoundsen_US
dc.titleSynthesis, characterization, and condensation reactions of some new (silylamino)phosphines and N-silylphosphoraniminesen_US
dc.typeTexten_US
etd.degree.departmentDepartment of Chemistry
etd.degree.levelDoctoral
local.collegeCollege of Science and Engineering
local.departmentChemistry and Biochemistry
local.academicunitDepartment of Chemistry
dc.type.genreDissertation
local.subjectareaChemistry and Biochemistry
dc.identifier.callnumberMain Stacks: AS38 .S268 (Regular Loan)
dc.identifier.callnumberSpecial Collections: AS38 .S268 (Non-Circulating)
etd.degree.nameDoctor of Philosophy
etd.degree.grantorTexas Christian University


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