| dc.description.abstract | The main goal of this PhD thesis has been providing a computational support to the development of
new or better performing catalysts, leading to the synthesis of new materials.
In this context, it is worth remembering that catalysis is a topic of primary relevance in the academy
as well as in the industry, due to the enormous impact of catalysis in every day life.
In particular, within this PhD project, attention has focused on catalytic systems based on Nheterocyclic
carbene (NHC) ligands, which have emerged as useful ligands in the last ten years.
In the first part of this thesis, the development of new molecular descriptors for the quantification of
steric and electronic effects in transition metal based catalysts has been pursued.
The final goal of this approach consists in rationalizing the highly disorganized and chaotic catalytic
space, to orientate experimental efforts towards possibly well performing catalysts, and away from
the ineffective ones. This would allow to pursue a catalysis by design approach, in alternative to the
“trial and error” classical approach.
In particular, descriptors based on topographic steric maps have emerged as powerful tools that can
be easily used and interpreted by the scientific community.
A user friendly web server has been implemented in order to allow the scientific community to
build steric maps for the systems of interest. The web server has already achieved great success
with a number of visitors all around the world.
In the second part of the thesis, attention was focused on developing and rationalizing new catalysts
in strict collaboration with experimental groups.
The systems investigated represent advanced application of N-heterocyclic carbenes as ligand in
Ru-catalyzed olefin metathesis, Pd-catalyzed C-C cross coupling reactions, and as catalysts in the
organopolymerization of polar olefins.
The detailed mechanistic studies have offered a comprehensive understanding of the whole
mechanisms, an achievement almost impossible to achieve with experimental techniques only.
The studies described in this work demonstrated that computational techniques can be of enormous
value to screen novel catalyst architectures more rapidly, and to obtain insights that could help in
the design and experimental synthesis of novel and improved catalysts. [edited by author] | en_US |
