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dc.contributor.advisorNeilson, Robert H.
dc.contributor.authorJi, Junminen_US
dc.date.accessioned2019-10-11T15:10:03Z
dc.date.available2019-10-11T15:10:03Z
dc.date.created1995en_US
dc.date.issued1995en_US
dc.identifieraleph-724555en_US
dc.identifierMicrofilm Diss. 654.en_US
dc.identifier.urihttps://repository.tcu.edu/handle/116099117/31819
dc.description.abstractN-Silylphosphoranimines of the type Me$\sb3$SiN=PR$\sb2$X (X = Br, Cl, OPh, and OCH$\sb2$CF$\sb3$) undergo condensation polymerization to cyclic and polymeric phosphazenes. In addition to this polymerization process, they also exhibit three other modes of reactivity: (1) nucleophilic substitution at the P-X site, (2) deprotonation-substitution reaction at the P-methyl group, and (3) silicon-nitrogen bond cleavage reaction. In order to further expand the scope of the derivative chemistry of N-silylphosphoranimines, especially the silicon-nitrogen bond cleavage reaction, a methodology has been developed to convert the N-silylphosphoranimines (I) to the corresponding anions (II). From these anions a series of novel acyclic (N-silyl)diphosphazenes (III) have been prepared. Preliminary studies of the reactivity of these (N-silyl)diphosphazenes indicated that thermolysis of these diphosphazenes affords new polymeric (IV) and/or cyclic (V) phosphazenes with very well-defined substituent pattems. These diphosphazenes also readily undergo hydrolysis to yield new types of N-phosphorylphosphoranimines (VI) which retain the intact -N-P=N-P= skeleton. Initial studies of reactions of CH$\sb3$CH$\sb2$OH with N-silylphosphoranimines led to a new route to (alkyl/aryl)cyclophosphazene trimers such as compound (VII). The molecular structures of several of these new cyclic phosphazenes (V and VII) and N-phosphorylphosphoranimines (VI) have been determined by single-crystal X-ray diffraction studies.
dc.format.extentix, 172 leaves : illustrationsen_US
dc.format.mediumFormat: Printen_US
dc.language.isoengen_US
dc.relation.ispartofTexas Christian University dissertationen_US
dc.relation.ispartofAS38.J485en_US
dc.subject.lcshSilicon compoundsen_US
dc.subject.lcshPhosphorus compoundsen_US
dc.subject.lcshPolymerizationen_US
dc.titleSynthesis, characterization, and reactivity of (N-Silyl)diphosphazenesen_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 .J485 (Regular Loan)
dc.identifier.callnumberSpecial Collections: AS38 .J485 (Non-Circulating)
etd.degree.nameDoctor of Philosophy
etd.degree.grantorTexas Christian University


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