Lee, Zhong Han Richmond
Description
Chemical manipulation of carbon-carbon bond is an expansive
subject and overarching theme in chemistry. By all accounts, it
takes a broad and concerted experimental and theoretical effort
in order to fully comprehend the nature of this chemical bond
that is virtually omnipresent in most important molecules.
Developing a more intimate understanding and appreciation of the
stability and reactivity of carbon-carbon bonds through quantum
chemical calculations is...[Show more] therefore the main theme and driver of
this thesis.
In this thesis, computational quantum chemistry was employed as
the tool to assist in the mechanistic investigation of C=C and
C-C bond oxidation by environmental oxidants (O3 and O2) and the
associated peroxyl ROO• self-reaction chemistry, copper
catalysed aerobic photo-oxidation of double, triple and single
carbon-carbon bonds, the stereoselective and chemo-divergent
construction of C-C bonds, and rhodium catalysed C-C(O) bond
formation in Metal Organic Frameworks. It was also used to
examine why C-C bonds were not formed during the termination
process of radical polymerisation of polyacrylates and
decomposition of RAFT-based polymers. The scope of this work is
wide but is just the tip of the iceberg on carbon-carbon bond
chemistry.
This thesis consists of 11 written manuscripts, and is
categorised into two parts. The first part focuses on
carbon-carbon bond cleavage and oxidative transformation to C(O),
so termed ‘oxidative reconstruction’, and the second part on
carbon-carbon bond generation or construction in a stereo and
chemo-specific manner. To achieve these research goals, extensive
and appropiately benchmarked quantum chemical calculations were
used to paint an insightful mechanistic picture of the reactions
mentioned, which went beyond simply capturing knowledge of the
reactivities and properties of carbon-carbon bonds, but also
provided clarifications to experiments, and allowed one to make
perceptive chemical predictions.
This thesis highlights the important role of theory in allowing
new scientific ideas to prosper, for instance updating reaction
mechanisms that conform to new experimental observations,
enabling better catalysts to be designed and strategies to
preserve the durability of polymers. In hindsight, each work and
chapter strives to take further steps toward bridging gaps in our
knowledge of carbon-carbon bond chemistry.
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