Fundamental Chemistry of Chlorophosphazenes and Polysilanes

Fundamental Chemistry of Chlorophosphazenes and Polysilanes

Bibliographic Details
Main Author: Stiel, Jason A.
Language:English
Published: University of Akron / OhioLINK 2016
Subjects:
Chemistry
Phosphazenes
superacid
polysilane
NMR monitoring polymerization
Online Access:http://rave.ohiolink.edu/etdc/view?acc_num=akron1467990664
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spelling ndltd-OhioLink-oai-etd.ohiolink.edu-akron14679906642021-08-03T06:37:20Z Fundamental Chemistry of Chlorophosphazenes and Polysilanes Stiel, Jason A. Chemistry Phosphazenes superacid polysilane NMR monitoring polymerization Polyphosphazenes and polysilanes make up two of the three largest classes of inorganic backbone polymers. Polyphosphazenes were first synthesized by Stokes over 100 years ago, and now they make up a library of over 700 different polymers. The major advantage polyphosphazenes have over organic polymers is that almost all polyphosphazenes are derived from the same parent polymer [PCl2N]n. However, polyphosphazenes have yet to be used commercially due to the irreproducibilities and high cost in the synthesis of [PCl2N]n. Polysilanes have interesting bonding characteristic due to a s*- delocalization along the silicon backbone, but this delocalization is still not fully understood. The main commercial use for polysilanes is as a fibrous silicon carbide precursor. This application does not take advantage of this unique delocalization of the polymer. More fundamental research is needed to advance the bonding characteristic of the silicon backbone. Throughout the literature, this delocalization has often been compared to conjugated carbon p system, and if this is true it should for Si to interact with electron rich metals. Fundamental chemistry associated with the ring-opening polymerization (ROP) of [PCl2N]3 is the main focuses of this dissertation, where the initial step of ROP and the superacidity of perchlorinated group 13 & 15 Lewis acids are explored. This dissertation is divided into five chapters: introduction, examining the mechanism of the ROP, determining the relative strength and stability of group 13 & 15 Lewis acids, an introduction and exploration into the bonding characteristic of the s*- delocalization of polysilane, and a conclusion. Chapter I will provide an overview of the chemistry of polyphosphazenes. Chapter II is an investigation into the possible species and steps in the ROP of [PCl2N]3 and into the effects of initiators on the process by 31P NMR. In chapter III, the relative superacidities of perchlorinated group 13 & 15 Lewis acids is discussed with emphases on PCl5. Chapter IV is an overview of polysilanes and an examination of the s*-delocalization of polysilane through entrapment of transition metals in cyclosilanes. Chapter V is the conclusions of this dissertation. 2016-10-04 English text University of Akron / OhioLINK http://rave.ohiolink.edu/etdc/view?acc_num=akron1467990664 http://rave.ohiolink.edu/etdc/view?acc_num=akron1467990664 unrestricted This thesis or dissertation is protected by copyright: all rights reserved. It may not be copied or redistributed beyond the terms of applicable copyright laws.
collection NDLTD
language English
sources NDLTD
topic Chemistry
Phosphazenes
superacid
polysilane
NMR monitoring polymerization
spellingShingle Chemistry
Phosphazenes
superacid
polysilane
NMR monitoring polymerization
Stiel, Jason A.
Fundamental Chemistry of Chlorophosphazenes and Polysilanes
author Stiel, Jason A.
author_facet Stiel, Jason A.
author_sort Stiel, Jason A.
title Fundamental Chemistry of Chlorophosphazenes and Polysilanes
title_short Fundamental Chemistry of Chlorophosphazenes and Polysilanes
title_full Fundamental Chemistry of Chlorophosphazenes and Polysilanes
title_fullStr Fundamental Chemistry of Chlorophosphazenes and Polysilanes
title_full_unstemmed Fundamental Chemistry of Chlorophosphazenes and Polysilanes
title_sort fundamental chemistry of chlorophosphazenes and polysilanes
publisher University of Akron / OhioLINK
publishDate 2016
url http://rave.ohiolink.edu/etdc/view?acc_num=akron1467990664
work_keys_str_mv AT stieljasona fundamentalchemistryofchlorophosphazenesandpolysilanes
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