Use this URL to cite or link to this record in EThOS:
Title: Mechanistic studies on the role of cationic palladium hydride initiators in addition polymerization of exo-and endo-functionalized norbornenes
Author: Cooper, Alan Thomas
Awarding Body: Durham University
Current Institution: Durham University
Date of Award: 2008
Availability of Full Text:
Access from EThOS:
Access from Institution:
The key bicyclic carbons within the monomer structures displayed no regular or consistent trends in (^13)C NMR signal shifts, upon the methylene spacing of the –CO(_2)TMS, -OMe, -NHSO(_2)CF(_3) and –Oac functionalities. Theoretical calculations are performed on isolated molecules of endo- and exo-NB-(CH(_2))(_n)C0(_2)H, where n = 0, 1 and 2, using the Gaussian 03 program, to rationalise the effects of introducing methylene spacers between norbornene and its functional group. The relationships between polymerisation activity and bond lengths, bond angles and Mulliken atomic charges are examined. Although the relationships shown for the exo-regioisomers differ from those occurring in the analogous endo-regioisomers, the main structural changes for both regioisomers involve the C3, C4, C5 and perhaps C6, atoms, which is not surprising given that these carbon atoms are nearest the electron withdrawing substituent. The structural changes occurring could not be used to explain the monomers changes in polymerisation activity.
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available