The DiMoCat group is an interdisciplinary group of research of the IQCC of the University of Girona
Theoretical and computational subgroup
The research of the theoretical and computational subgroup is devoted to the computational studies of reaction mechanisms, new methodological developments and analysis of the chemical bond.
1. Computational studies of reaction mechanisms
Reactivity of fullerenes, endohedral metallofullerenes, and nanotubes. We are particularly interested in the regioselectivity and the reaction mechanism of cycloadditions to fullerenes, endohedral metallofullerenes, and nanotubes catalyzed by transition metals, such as the [2+2+2] or the [2+2+1] Pauson-Khand cycloadditions. The possibility that the products produced can be used in photovoltaic cells is usually analyzed.
Organometallic reactions. Among them those which involve metal carbenes like iron carbenes or rhodium carbenes. The process of oxidation of water catalyzed by transition metals for the production of hydrogen is also of interest for us. The main aim is to design new catalysts that are able to make studied reactions more efficiently.
2. New methodological developments
Nonlinear optical properties (NLOP). The objective is to develop new density functionals that improve current methods to determine NLOPs.
New approaches to the functional correlation-exchange based on the behavior of confined atoms. It is possible to develop almost exact correlation-exchange potentials for spherically confined atoms. These potentials can be used to propose new functional DFT correlation-exchange.
3. Study of the chemical bond
Aromaticity studies. We have been developing new methods for quantifying aromaticity and we are applying them to systems with three-dimensional aromaticity, metalloaromaticity, and aromaticity in excited states. For the excited state aromaticity, we investigate its effect on the photophysics and photochemistry of the systems studied.
Resonant Assisted Hydrogen Bonds (RAHB). RAHBs are stronger than conventional hydrogen bonds due to the partial delocalization of π-electrons. The effect is especially interesting when aromatic rings intervene in the RAHB.
The research of the theoretical and computational subgroup is devoted to the C-C and C-X bond formation catalyzed by transition metals with the following sublines:
1. Cyclization reactions catalyzed by transition metals
Cycloaddition reactions catalyzed by Rh of unsaturated substrates. We are particularly interested in the cycloaddition reactions involving allenes. We are interested in controlling the regioselectivity – which of its double bonds reacts – to master the the construction of various products from one single substrate. The stereoselectivity of the processes is always studied. We are also interested in the functionalization of fullerenes through transition metal-catalyzed cycloaddition reactions. The ultimate goal is to synthesize compounds with applications in the fields of material science and nanotechnology.
Cyclization reactions through Rh(I)-carbene intermediates. Cascade reactions are developed using as a key step the carbene alkyne metathesis that generates Rh(I) vinylcarbenes that can be trapped in typical reactions of carbenes (X-H activations, cyclopropanations) stereoselectively. The stereoselectivity of the processes is always studied.
2. Biomimetic supramolecular catalysis.
Carbocycle reactions inspired by terpene cyclizations. In the biosynthesis of cyclic terpenes, complex carbocyclic structures are obtained in an easy and effective way using simple linear polyenic precursors. These compounds have great pharmacological relevance and also as fragrances or biocontrol agents, but their synthesis by conventional methods is difficult and inefficient. Taking advantage of the knowledge developed in recent years in the preparation of synthetic receptors, carbocation cyclization reactions inspired by terpenic cyclizations are carried out, using these receptors as biomimetic catalysts.