Two new fellowships to Alex Díaz and Cristina Castanyer, PhD researchers in training

This week we have known that Alex Díaz has got the prestigious FPU fellowship of the Spanish Ministerio de Educación and Cristina Castanyer has got the FPI fellowship that the Spanish Ministerio de Ciencia awarded to the project CTQ2017-85341-P lead by Anna Pla and Miquel Solà. Alex Díaz is already a research in training supervised by Anna Pla and Anna Roglans and he is working on cyclization reactions catalized by Rh carbenes. Cristina Castanyer will start her PhD supervised by Anna Pla and Miquel Solà and she will work on [2+2+2] cycloadditions to fullerenes.

Congratulations to Àlex and Cristina!

Angew. Chem. Int. Ed. Inside Cover describing the first All-fullerene Electron Donor-Acceptor Conjugates

Photoinduced electron transfer (PET) is a general nature occurring process which is related with the photosynthetic process. Scientists have always been interested in mimicking this process from artificial molecules in the search for controlling and tuning this process for practical purposes. The appropriate molecules and materials have been an important task in science. The aforementioned mimicking of the photosynthetic process requires the presence of appropriate electron donor molecules interacting (covalently or supramolecularly) with electron acceptor molecules. Light irradiation promotes the electron transfer from the donor to the acceptor units. Fullerenes are amazing ball-shape molecules formed exclusively by carbon atoms which are known to exhibit interesting electron accepting properties. Therefore, they have been extensively used in Donor-Acceptor systems.

A group of chemists from the Universidad Complutense de Madrid lead by Prof. Nazario Martín together with a group of researchers from the Friederich-Alexander Univesität Erlangen-Nürnberg lead by Dirk M. Guldi, and the DiMoCat members Antony J. Stasyuk, Olga A. Stasyuk, Alexander A. Voityuk, and Miquel Solà have shown the first example in which fullerenes, depending on their features, are able to act as acceptor but also as donor components in artificial photosynthetic systems. Furthermore, they have described the first example in which light irradiation promotes de electron transfer from the donor Lu3N@C80 to the acceptor C60 giving rise to a charge separated state involving two fullerene cages!

The paper has been published in Angew. Chem. Int. Ed. And can be found in the following link Angew. Chem. Int. Ed., 58 (2019) 6932-6937. The inside cover of the issue has been dedicated to this work:

Generation of H2 by an Environmental Friendly Mn-Catalyzed Reaction

A pure computational paper by the DIMOCAT team of IQCC has been undertaken to favour the generation of H2  , once known experimentally by Milstein and coworkers that Mn-pincer could catalyze the acceptorless dehydrogenative coupling of nitriles and alcohols to yield acrylonitriles. The reaction mechanism proposed in that work contained some intermediates that, in most of the cases, were not characterized. Moreover, one of the intermediates involved a charged separation, which is unlikely in apolar solvents. To clarify the reaction mechanism of this critical reaction, a DFT study was performed. Results prove the existence of a cooperative effect of the metal and the ligand in several steps of the catalytic cycle. It is unveiled the presence of several equilibria between isomeric intermediates where water, or the same alcohol reagent, takes part in assisting the proton transfer. Furthermore, the charge-separated structure proposed experimentally turned out to be a nearly pure covalent bond between the two expected charged moieties. More importantly catalytically speaking, the Knoevenagel condensation step that generates the acrylonitrile is found to be the rate-determining step.

J. A. Luque-Urrutia, M. Solà, D. Milstein, and A. Poater

“Mechanism of the Manganese-Pincer Catalyzed Acceptorless Dehydrogenative Coupling of Nitriles and Alcohols”

J. Am. Chem. Soc. 2019, ASAP, accepted

DOI: 10.1021/jacs.8b11308