Continuing an exploration of the mechanism of this reaction, an alternative new mechanism was suggested in 1989 (having been first submitted to the journal ten years earlier!).[cite]10.1002/jhet.5570260518[/cite] Here the key intermediate proposed is a thiirenium cation (labelled 8 in the article) and labelled Int3 below.

Sometimes a (scientific) thought just pops into one’s mind. Most are probably best not shared with anyone, but since its the summer silly season, I thought I might with this one. Famously, according to Einstein, m  = E/c^^2, the equivalence of energy to mass. Consider a typical exoenergic chemical reaction:  A → B, ΔG -100 kJ/mol.

The Willgerodt reaction[cite]10.1002/cber.18870200278[/cite], discovered in 1887 and shown below, represents a transformation with a once famously obscure mechanism. A major step in the elucidation of that mechanism came[cite]10.1021/ja01157a034[/cite] using the then new technique of ¹⁴ C radio-labelling, shortly after the atom bomb projects during WWII made ¹⁴ CO ₂ readily available to researchers.

One of the most fascinating and important articles dealing with curly arrows I have seen is that by Klein and Knizia on the topic of C-H bond activations using an iron catalyst.[cite]10.1002/anie.201805511[/cite] These are so-called high spin systems with unpaired electrons and the mechanism of C-H activation involves both double headed (two electron) and fish-hook (single electron) movement.

Metaldehyde is an insecticide used to control slugs.

With the current global lockdown, and students along with everyone else staying at home, I have noticed some old posts of mine are getting more attention than normal.

My previous two posts on the topic of strongest bonds have involved mono and diprotonating N ₂ and using quantum mechanics to predict the effect this has on the N-N bond via its length and vibrational stetching mode. Such species are very unlikely to be easily observed for verification.

I occasionally notice that posts that first appeared here many years ago suddenly attract attention.

Earlier, I explored the choreography or “timing”, of what might be described as the curly arrows for a typical taught reaction mechanism, the 1,4-addition of a nucleophile to an unsaturated carbonyl compound (scheme 1). I am now going to explore the consequences of changing one of the actors by adding the nucleophile to an unsaturated imine rather than carbonyl compound (scheme 2).  **

A little more than a year ago, a ChemRxiv pre-print appeared bearing the title referenced in this post,[cite]10.26434/chemrxiv.8009633.v1[/cite] which immediately piqued my curiosity. The report presented persuasive evidence, in the form of trapping experiments, that dicarbon or C ₂ had been formed by the following chemical synthesis.

In a previous post, I talked about a library of reaction pathway intrinsic reaction coordinates (IRCs) containing 115 examples of organic and organometallic reactions. Now (thanks Dean!) I have been alerted to a brand new databank of dynamics trajectories (DDT), with the focus on those reactions taught in undergraduate organic chemistry courses, some of which are shown below.