Knychala, Jonathan Paul (1987)
The synthesis and properties of some metallocene containing macrocycles and their analogues.
Full text access: Open
The objectives of this work were (i) to prepare a number of mono- and bi-cyclic cryptands in which one of the bridges is either a ferrocene or ruthenocene unit and (ii) to investigate the properties of these compounds by a variety of techniques with a view to assessing their ion-binding selectivity and electronic interactions which might occur between the metallocene moiety and the bound metal ion.
The macro bi-cycles were prepared from the parent metallocenes by a number of synthetic routes. The 1,1'-disubstituted ferrocene and ruthenocene were investigated; these materials were then converted by established pathways to the target molecules. Inter-mediates and the final products of these preparations were fully characterised by a wide variety of spectroscopic and other techniques. Particular attention was paid to the temperature dependence of the n.m.r. spectra of the cryptands themselves, which showed remarkable flexibility. The energetics of these processes were investigated.
The final cyclic reactions leading to the cryptands also afforded in each case quantities of dimeric material which were also isolated and characterized. Some initial investigations were also carried out on the ion-binding properties of these materials.
These cryptands offer the possibility of significant electronic interaction between the metallocene unit and the included metal ion, in such a manner that the degree and nature of the ion-binding may be externally detected. The efficiency of this process relies on the electronic properties of the metallocene itself and these have therefore been investigated by a number of techniques including cyclic voltammetry and photo electron spectroscopy.
This is a Accepted version
This version's date is:
is not peer reviewed
Deposited by () on
in Royal Holloway Research Online.Last modified on 01-Feb-2017
Digitised in partnership with ProQuest, 2015-2016.
Institution: University of London, Bedford College (United Kingdom).