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Title: The chemistry of some heavy transition metal organometallics
Author: Adams, C.
Awarding Body: University of Cambridge
Current Institution: University of Cambridge
Date of Award: 1999
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The thesis is concerned with the synthesis of some new organometallic and co-ordination compounds of platinum (in the main), tungsten and gold. Chapter 1 contains an overview of the field of platinum σ - acetylide chemistry from its origins to the present day, looking at structural types and the properties of this kind of compound. Chapter 2 contains details of the synthesis and characterisation of some novel bipyridyl containing platinum acetylides of the form cis-(tbu2bipy)Pt(-C≍C-R)2 (where R = Ph.p-C6H4-CH3, SiMe3, p-C6H4-NO2 and tbu2bipy = 4,4'-bis(tbutyl)-2,2'-bipyridine), looking at the IR, UV and NMR spectroscopy of these compounds and at the crystal structure of a representative member of this class. Some EHMO calculations pertaining to the HOMO and the LUMO of these compounds are presented, and EPR and in-situ spectroelectrochemical experiments that support these MO calculations are detailed. There is also a report on and a discussion of the attempted synthesis of some molecular squares. Chapter 3 looks at the use of the compounds detailed in Chapter 2 as chelating agents for copper and silver thiocyanate, tetrafluoroborate and perchlorate salts. The crystal structures of representatives of these are investigated, as is their electro-and spectro- chemical behaviour. Chapter 4 contains details of some new bis-pyridyl platinum acetylides of formula (npy)2Pt(-C≍C-R)2 (npy = 4-(5-nonylpyridine)), in which the platinum atom has mutually trans - acetylide ligands, and some polymeric species formed from these monomeric precursors and bis - acetylides containing chromophoric groups (bithiophene, terthophene and 9-fluorenone) are presented, and their optical and electronic properties investigated.
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available