St Andrews Research Repository

St Andrews University Home
View Item 
  •   St Andrews Research Repository
  • Chemistry (School of)
  • Chemistry
  • Chemistry Theses
  • View Item
  •   St Andrews Research Repository
  • Chemistry (School of)
  • Chemistry
  • Chemistry Theses
  • View Item
  •   St Andrews Research Repository
  • Chemistry (School of)
  • Chemistry
  • Chemistry Theses
  • View Item
  • Login
JavaScript is disabled for your browser. Some features of this site may not work without it.

Some aspects of the molecular structure of heterocyclic and organometallic compounds

Thumbnail
View/Open
AlastairCuthbertsonPhDThesis.pdf (39.36Mb)
Date
1983
Author
Cutherbertson, Alastair Fraser
Supervisor
Glidewell, Christopher
Metadata
Show full item record
Altmetrics Handle Statistics
Abstract
Various rules which have been used to rationalise molecular geometries are discussed. After this the results from MNDO calculations on simple carbenes, ethers and amines are presented, and these were designed to test the hypothesis that in the presence of ligands of low electronegativity lone pairs would not fulfil their stereochemical role assigned to them in the VSEPR model. Following on are MNDO calculations on cyclic molecules: the cyclopentadiene ring is planar in silylcyclopentadiene and non-planar in trimethylsilylcyclopentadiene. The calculations attempt to resolve this and in addition the nature of the fluxional exchange. The intermediates which are formed by diazepinium salts when they are protodebrominated are then discussed in the light of MNDO calculations. Single crystal x-ray work was carried out for four heterocyclic molecules. The compounds reported are: 4-phenyl-3-phenylamino-1,2,4-thiadiazolin-5-one; 5-(N-methylthiocarbamoylimino)-4-phenyl-3-phenylamino-4H-l,2,4-thiadiazoline; N,N-bis[2-(5-t-butyl-3H-1,2-dithiol-3-ylidene)ethylidene]hydrazine and N,N-dimethyl-N-[2-(5-t-butyl-3H-1,2-dithiol-3-ylidene)ethylidene]hydrazine. Details of MNDO calculations which were undertaken on molecules related to the x-ray work are then presented, and in the final chapter a discussion of the heterocyclic crystal structures appears. The first appendix reports the structure of a macrocyclic ligand, the second provides a list of publications and the third appendix is a list of the structure factors, least-squares planes and anisotropic temperature parameters for the crystal structure determinations.
Type
Thesis, PhD Doctor of Philosophy
Collections
  • Chemistry Theses
URI
http://hdl.handle.net/10023/15289

Items in the St Andrews Research Repository are protected by copyright, with all rights reserved, unless otherwise indicated.

Advanced Search

Browse

All of RepositoryCommunities & CollectionsBy Issue DateNamesTitlesSubjectsClassificationTypeFunderThis CollectionBy Issue DateNamesTitlesSubjectsClassificationTypeFunder

My Account

Login

Open Access

To find out how you can benefit from open access to research, see our library web pages and Open Access blog. For open access help contact: openaccess@st-andrews.ac.uk.

Accessibility

Read our Accessibility statement.

How to submit research papers

The full text of research papers can be submitted to the repository via Pure, the University's research information system. For help see our guide: How to deposit in Pure.

Electronic thesis deposit

Help with deposit.

Repository help

For repository help contact: Digital-Repository@st-andrews.ac.uk.

Give Feedback

Cookie policy

This site may use cookies. Please see Terms and Conditions.

Usage statistics

COUNTER-compliant statistics on downloads from the repository are available from the IRUS-UK Service. Contact us for information.

© University of St Andrews Library

University of St Andrews is a charity registered in Scotland, No SC013532.

  • Facebook
  • Twitter