An international group of researchers led by Dr. Warren E. Piers (University of Calgary) and Dr. Heikki M. Tuononen (University of Jyväskylä) has been able to isolate and characterize an important chemical intermediate whose existence has, so far, only been inferred from indirect experimental evidence.
Chemical reactions rarely go from starting materials to final products in one single step, but instead they progress through a number of intermediates. In many cases the intermediates are not stable enough to be studied by conventional characterization methods, which thwarts efforts to understand reaction mechanisms.
In the present case, the research group of Dr. Piers was able to undertake a comprehensive solution and solid-state characterization of an adduct between a Lewis acidic perfluoroarylborane and an electron-rich silane that has been postulated to be an intermediate in the 'frustrated' Lewis-pair hydrosilylation of C=C, C=O and C=N double bonds.
"The results of this paper are important because we now know more about the mechanistic details of a significant chemical reaction," says Dr. Piers, a Tier I Canada Research Chair at the University of Calgary. "It is like travelling along the trans-Canada highway from Victoria to St. John's always blindfolded and finally being able to see the Rockies along the way: a breathtaking moment," he explains.
However, characterizing an important reaction intermediate is only half of the story. Equally important is to understand what factors contribute to its stability and by how much. Here the research group of Academy Research Fellow Dr. Tuononen comes into play with the tools of theoretical modelling.
"Computational work showed that this is a good example of the Goldilocks effect in chemistry: everything needs to be 'just right'," tells Dr. Tuononen. "The calculations not only pinpoint the important contributors to the stability but also enable us to use this information to design similar adducts that are even more stable. This way we can study them experimentally in greater detail for further insight into the underlying chemistry."
"Direct observation of a borane–silane complex involved in frustrated Lewis-pair-mediated hydrosilylations" by Adrian Y. Houghton, Juha Hurmalainen, Akseli Mansikkamäki, Warren E. Piers and Heikki M. Tuononen was published online in Nature Chemistry on September 28th, 2014. http://dx.doi.org/10.1038/nchem.2063
Picture: Formation of the reactive borane-silane adduct at -80Celcius is indicated by a color change © Adrian Houghton. Artistic impression of the adduct © Akseli Mansikkamäki
Funding for the work was provided by the Natural Sciences and Engineering Research Council of Canada (W.E.P.) and the Academy of Finland (H.M.T.).
Dr. Heikki M. Tuononen | Eurek Alert!
Ion treatments for cardiac arrhythmia — Non-invasive alternative to catheter-based surgery
20.01.2017 | GSI Helmholtzzentrum für Schwerionenforschung GmbH
Seeking structure with metagenome sequences
20.01.2017 | DOE/Joint Genome Institute
An important step towards a completely new experimental access to quantum physics has been made at University of Konstanz. The team of scientists headed by...
Yersiniae cause severe intestinal infections. Studies using Yersinia pseudotuberculosis as a model organism aim to elucidate the infection mechanisms of these...
Researchers from the University of Hamburg in Germany, in collaboration with colleagues from the University of Aarhus in Denmark, have synthesized a new superconducting material by growing a few layers of an antiferromagnetic transition-metal chalcogenide on a bismuth-based topological insulator, both being non-superconducting materials.
While superconductivity and magnetism are generally believed to be mutually exclusive, surprisingly, in this new material, superconducting correlations...
Laser-driving of semimetals allows creating novel quasiparticle states within condensed matter systems and switching between different states on ultrafast time scales
Studying properties of fundamental particles in condensed matter systems is a promising approach to quantum field theory. Quasiparticles offer the opportunity...
Among the general public, solar thermal energy is currently associated with dark blue, rectangular collectors on building roofs. Technologies are needed for aesthetically high quality architecture which offer the architect more room for manoeuvre when it comes to low- and plus-energy buildings. With the “ArKol” project, researchers at Fraunhofer ISE together with partners are currently developing two façade collectors for solar thermal energy generation, which permit a high degree of design flexibility: a strip collector for opaque façade sections and a solar thermal blind for transparent sections. The current state of the two developments will be presented at the BAU 2017 trade fair.
As part of the “ArKol – development of architecturally highly integrated façade collectors with heat pipes” project, Fraunhofer ISE together with its partners...
19.01.2017 | Event News
10.01.2017 | Event News
09.01.2017 | Event News
20.01.2017 | Awards Funding
20.01.2017 | Materials Sciences
20.01.2017 | Life Sciences