Is asking a question such as “what is the smallest angle subtended at a chain of three connected 4-coordinate carbon atoms” just seeking another chemical record, or could it unearth interesting chemistry?
The smallest C-C-C angle?
October 31st, 2016An inorganic double helix: SnIP.
October 16th, 2016After sixty years of searching, the first non-templated double helical carbon-free inorganic molecular structure has been reported.[cite]10.1002/adma.201603135[/cite] That is so neat that I thought to load the 3D coordinates here for you to interact with and then to explore the prospect of using these coordinates to add some value with e.g. some chiroptical calculations.
Catenated atoms and groups.
October 13th, 2016Chemists are as fond of records as any, although I doubt you will find many chemical ones in the Guinness world records list. Polytriangulanes chase how many cyclopropyl 3-rings can be joined via a vertex. Steve Bachrach on his blog reports some recent work by Peter Schreiner and colleagues[cite]10.1021/acs.jctc.6b00669[/cite] and the record for catenation of such rings appears to be 15. This led me to think about some other common atoms and groups. Here I have searched for crystal structures only; there may be examples of course for which no such data has been reported.
σ or π nucleophilic reactivity of imines? A mechanistic reality check using substituents.
October 9th, 2016Previously, a mechanistic twist to the oxidation of imines using peracid had emerged. Time to see how substituents respond to this mechanism.
σ or π nucleophilic reactivity of imines? A mechanistic twist emerges.
September 28th, 2016The story so far. Imines react with a peracid to form either a nitrone (σ-nucleophile) or an oxaziridine (π-nucleophile).[cite]10.1016/S0040-4039(00)98582-4[/cite] The balance between the two is on an experimental knife-edge, being strongly influenced by substituents on the imine. Modelling these reactions using the “normal” mechanism for peracid oxidation did not reproduce this knife-edge, with ΔΔG (π-σ) 16.2 kcal/mol being rather too far from a fine balance.
More stereoelectronics galore: hexamethylene triperoxide diamine.
September 22nd, 2016Compounds with O-O bonds often have weird properties. For example, artemisinin, which has some fascinating stereoelectronics. Here is another such, recently in the news and known as HMTD (hexamethylene triperoxide diamine). The crystal structure was reported some time ago[cite]10.1021/jp0123841[/cite] and the article included an inspection of the computed wavefunction. However this did not look at the potential stereoelectronics in this species, which I now address here.
σ or π? The ambident nucleophilic reactivity of imines: crystallographic and computational reality checks.
September 21st, 2016Nucleophiles are species that seek to react with an electron deficient centre by donating a lone or a π-bond pair of electrons. The ambident variety has two or more such possible sources in the same molecule, an example of which might be hydroxylamine or H2NOH. I previously discussed how for this example, the energetics allow the nitrogen lone pair (Lp) to win out over the O Lp. Here, I play a similar game, but this time setting an NLp up against a π-pair.
What’s in a name? Stabilised “nitrenes”.
September 19th, 2016I previously explored stabilized “carbenes” with the formal structures (R2N)2C:, concluding that perhaps the alternative ionic representation R2N+=C–NR2 might reflect their structures better. Here I take a broader look at the “carbene” landscape before asking the question “what about nitrenes?”