dc.contributor.advisor | Neilson, Robert H. | |
dc.contributor.author | Ji, Junmin | en_US |
dc.date.accessioned | 2019-10-11T15:10:03Z | |
dc.date.available | 2019-10-11T15:10:03Z | |
dc.date.created | 1995 | en_US |
dc.date.issued | 1995 | en_US |
dc.identifier | aleph-724555 | en_US |
dc.identifier | Microfilm Diss. 654. | en_US |
dc.identifier.uri | https://repository.tcu.edu/handle/116099117/31819 | |
dc.description.abstract | N-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.extent | ix, 172 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.J485 | en_US |
dc.subject.lcsh | Silicon compounds | en_US |
dc.subject.lcsh | Phosphorus compounds | en_US |
dc.subject.lcsh | Polymerization | en_US |
dc.title | Synthesis, characterization, and reactivity of (N-Silyl)diphosphazenes | 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 .J485 (Regular Loan) | |
dc.identifier.callnumber | Special Collections: AS38 .J485 (Non-Circulating) | |
etd.degree.name | Doctor of Philosophy | |
etd.degree.grantor | Texas Christian University | |