Ewch i’r prif gynnwys
Athanasia Dervisi

Dr Athanasia Dervisi

Lecturer in Inorganic Chemistry

Ysgol Cemeg

Email
DervisiA@caerdydd.ac.uk
Telephone
+44 29208 74081

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Research Group:  Inorganic Chemistry

Research Interests

Dr Dervisi$acirc; s research interests include the synthesis and coordination of functionalised ligands, such as phosphines and NHC carbenes and their catalytic, biological and optoelectronic applications.  

Much of our ligand design takes inspiration from the hydrocarbon chiral pool (sugars in particular). Such ligands offer the advantages of predetermined backbone chirality with often rigid structure and high degree of peripheral functionalisation. As an example, chelating diphosphine and N-heterocyclic carbene ligands have been derived from D-isomannide, a mannitol dehydration product. In this case we have taken advantage of the predetermined backbone chirality of a naturally occurring polyol (mannitol) and have prepared highly functional ligands with multiple chiral centres in just two synthetic steps.

Another area of interest is the study of the electronic and steric properties of large ring (>5) N-heterocyclic carbene ligands. In this area we have contributed in the understanding of the factors affecting the stability of such NHC ligands and their applications in catalysis.

For more information, click on the 'Research' tab above.

Teaching

CH0001 Fundamental Aspects of Chemistry

CH3102 Foundations of Inorganic Chemistry

CH3104 Introduction to the Solid State and Applications of Spectroscopy

CH3302 Advanced Organometallic and Coordination Chemistry

CH3309 Placement Experience

CH2325 BSc Project

CH3402 Medicinal Inorganic Chemistry

Cyhoeddiad

2022

2018

2013

2012

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2010

2009

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1999

Erthyglau

Ymchwil

Research Interests

3.3.0 bicyclic ligand frameworks

An area currently pursued in the group is the study of phosphine ligands based on 3.3.0 bicyclic frameworks. This project fits with our broader interest in the design of more rigid, sterically controlled chiral ligands derived from the hydrocarbon chiral pool (sugars in particular). Such ligands offer the advantages of predetermined backbone chirality with often rigid structure and high degree of peripheral functionalisation. Chelating diphosphine ligands derived from D-isomannide 1, a mannitol dehydration product, and their TM complexes 2 have been isolated. In this case, we have taken advantage of the predetermined backbone chirality of a naturally occurring polyol (mannitol) and prepared chelating diphosphines with 4 chiral centres in only two steps. Presently, we are in the process of preparing NHC (N-heterocyclic carbene) precursors 3 based on the isomannide framework.

Fig 1

 Large ring N-heterocyclic Carbene Ligands

The strong s-donating properties of NHCs make them effective stabilizing ligands in organometallic chemistry as well as important ligands in some forms of catalysis.   To date research has largely focused on five-membered ring carbenes. Previously, we reported the first examples of novel, saturated, seven-membered diazepanylidene carbenes and their transition metal complexes, in collaboration with Fallis & Cavell.

A simple, versatile and high yielding route from amidines was also devised, leading to 6- and 7- membered carbenes (and saturated 5-membered NHCs).   This methodology allows the isolation of a range of carbenes, and hence metal complexes, which are not available via other routes.

Fig 2

Six-, and in particular, seven-membered ring carbenes are intriguing from several points of view.   They are very basic, somewhat more basic than the saturated 5-membered-ring carbenes, which are in turn more basic than their unsaturated counterparts. Structurally they also offer some unique features. The saturated seven-membered ring is highly twisted providing an opportunity to design new chiral ligand systems and the large heterocyclic rings lead to large N-CNHC-N angles.

Fig 3

Hybrid P,S ligand systems

In this area we are involved in the synthesis and catalytic applications of hybrid P,S ligands; studying the effect of bulky substituents on the P,S backbone in relation to co-ordination and catalysis. Previously, we have reported their applications in palladium-catalysed C-C coupling reactions. Some of these catalysts desirable features are: air and water stability, high tofs$acirc; and catalyst recyclability. Their water stability has enabled us to develop a biphasic Heck system where simple inorganic bases such as NaOH are used instead of organic bases.

Fig 4

Addysgu

Bywgraffiad

PhD Cardiff University (1997, P. G. Edwards). Postdoctoral Research Fellow, Vancouver (1997, M.D. Fryzuk), Bristol University (1998, R.W. Alder). Appointed as Lecturer, Cardiff, in 1999.

Member of the Royal Society of Chemistry and Honorary Secretary of the South East Wales RSC Section.

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