Redox and structural properties of transition metal dithioacetylacetonates and related complexes
dc.contributor.author
Anderson, Ian Hamilton
en
dc.date.accessioned
2018-01-31T11:15:28Z
dc.date.available
2018-01-31T11:15:28Z
dc.date.issued
1987
dc.description.abstract
en
dc.description.abstract
CHAPTER 1 provides a brief summary of the previously
reported electrochemical behaviour of metal bisdithiochelate complexes (X = Ai,Pd,Pt) and a general
outline of the topics discussed in each chapter of this
thesis.
en
dc.description.abstract
CHAPTER 2 initially describes the preparative routes to
the parent systems [M(S₂C₃RHR')₂] and [M(S₂CNR'₂)₂], followed by a detailed account of the syntheses of the
hybrid complexes [M(S₂C₃RHR')(S₂CNR"₂)] (M = Ni, Pd,Pt,R,R' = CH₃, Ph, CF₃; R' = CH₃, C₂H₅, i-C₃H₇, C₄H₉; but not
all possible combinations). Infra-red, nmr, electronic
and mass spectroscopic studies of these 1,1-dithio-1,3-
dithio complexes are also extensively reported.
en
dc.description.abstract
CHAPTER 3 is concerned with X-ray crystallographic studies
of [Ni (S₂C₉CH₃HCH3) (S₂CN (C₂H₅)₂)] and
[Ni (S₂C₃CF₃HCH₃)(S₂CN(i-C₃H₇)₂)]. These structural
results suggest that with the exception of the MS₄ core,
the geometric parameters of the (S₂C₃RHR') and (S₂CNR'₂)
hybrid moieties are relatively unaltered from those found
in the respective parent complexes [Ni(S₂C₃RHR")₂] and
[Ni (S₂CNR"₂)₂] .
en
dc.description.abstract
CHAPTER 4 discusses the voltammetric behaviour of the
hybrid systems [M(S₂C₃RHR')(S₂CNR"₂)], which all display
one isolated reversible reduction. Our electrochemical
data strongly supports predominant 1,3-dithio-ß-diketonate
character in the redox-active orbital involved in this
reduction.
en
dc.description.abstract
CHAPTER 5 describes the syntheses and spectroscopic
characterisations of the asymmetrically-substituted
systems [M(S₂C₃CF₃HCH₃)(S₂C₃CH₃HCH₃)] (M = Ni, Pd,Pt).
Voltammtric investigations, in conjunction with our
[M(S₂C₃RHR') (S₂CHR"₂) ]⁰/¹⁻ data, suggest that the two
observed one-electron ligand-mediated reductions of the
mixed complexes are, at least, consistent with localised
electron -acceptance.
en
dc.identifier.uri
http://hdl.handle.net/1842/26101
dc.publisher
The University of Edinburgh
en
dc.relation.ispartof
Annexe Thesis Digitisation Project 2017 Block 15
en
dc.relation.isreferencedby
en
dc.title
Redox and structural properties of transition metal dithioacetylacetonates and related complexes
en
dc.type
Thesis or Dissertation
en
dc.type.qualificationlevel
Doctoral
en
dc.type.qualificationname
PhD Doctor of Philosophy
en
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