“Because examples of this reaction are so rare, we wanted to understand why these cobalt complexes were special and how they worked in the reaction,” said Valerie Schmidt, lead author on the article and a postdoctoral researcher in the Chirik lab.
The new cobalt-catalyzed reaction overcame limitations that have plagued other similar methods, such as poor selectivity or requiring very reactive alkenes, which are chemical structures composed of two carbons joined by a double bond, as starting materials. The research team suspected their success came from certain molecules, called bis(imino)pyridine ligands, that are attached to the cobalt center and which are capable of passing electrons to and from the metal.
The Chirik group has used these redox active ligands previously, attached instead to iron to catalyze a [2π+2π] reaction reported in 2006. But the iron catalyst is highly sensitive to air and moisture, an issue that could be mitigated by switching to a less reactive metal like cobalt.
Replacing iron with cobalt presented a unique challenge in analysis because it altered the complex’s overall magnetic state from diamagnetic to paramagnetic. Unlike diamagnetic compounds, paramagnetic compounds can be difficult to identify by nuclear magnetic resonance (NMR) spectroscopy, a technique that uses a strong magnet to pulse atomic nuclei to reveal their environments, and a primary tool for characterizing molecules.
“We really had to be creative in finding ways to confirm our hypotheses about the catalyst,” Schmidt said. One extremely useful tool, analogous to nuclear magnetic resonance but that pulses electrons instead of nuclei, was electron paramagnetic resonance (EPR). This technique allowed the researchers to track the unpaired electrons, called radicals, throughout the reaction.
For the full story: https://blogs.princeton.edu/research/2015/06/09/putting-two-and-two-together-to-make-unexplored-chemicals-j-american-chemical-society/