Archive for the ‘Interesting chemistry’ Category

Molecule of the year (month/week)?

Monday, December 12th, 2016

Chemical and engineering news (C&EN) is asking people to vote for their molecule of the year from six highlighted candidates. This reminded me of the history of internet-based “molecules of the moment“. It is thought that the concept originated in December 1995 here at Imperial and in January 1996 at Bristol University by Paul May and we were joined by Karl Harrison at Oxford shortly thereafter. Quite a few more such sites followed this concept, differentiated by their time intervals of weeks, months or years. The genre is well suited for internet display because of plugins or “helpers” such as Rasmol, Chime, Jmol and now JSmol which allow the three dimensions of molecular structures to be explored by the reader. Here I discuss a second candidate from the C&EN list; a ferrocene-based Ferris wheel[cite]10.1038/nchem.2553[/cite],[cite]10.5517/CCDC.CSD.CC1JPKYQ[/cite] (DOI for 3D model: 10.5517/CCDC.CSD.CC1JPKYQ) originating from research carried out at Imperial by Tim Albrecht, Nick Long and colleagues.

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Long C=C bonds.

Thursday, December 1st, 2016

Following on from a search for long C-C bonds, here is the same repeated for C=C double bonds.

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Long C-C bonds.

Wednesday, November 30th, 2016

In an earlier post, I searched for small C-C-C angles, finding one example that was also accompanied by an apparently exceptionally long C-C bond (2.18Å). But this arose from highly unusual bonding giving rise not to a single bond order but one closer to one half! How long can a “normal” (i.e single) C-C bond get, a question which has long fascinated chemists.

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The largest C-C-C angle?

Tuesday, November 1st, 2016

I am now inverting the previous question by asking what is the largest angle subtended at a chain of three connected 4-coordinate carbon atoms? Let’s see if further interesting chemistry can be unearthed.

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More stereoelectronics galore: hexamethylene triperoxide diamine.

Thursday, September 22nd, 2016

Compounds 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.

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A periodic table for anomeric centres, this time with quantified interactions.

Monday, August 8th, 2016

The previous post contained an exploration of the anomeric effect as it occurs at an atom centre X for which the effect is manifest in crystal structures. Here I quantify the effect, by selecting the test molecule MeO-X-OMe, where X is of two types:

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A periodic table for anomeric centres.

Saturday, August 6th, 2016

In the last few posts, I have explored the anomeric effect as it occurs at an atom centre X. Here I try to summarise the atoms for which the effect is manifest in crystal structures.

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Stereoelectronic effects galore: bis(trifluoromethyl)trioxide.

Thursday, August 4th, 2016

Here is a little molecule that can be said to be pretty electron rich. There are lots of lone pairs present, and not a few electron-deficient σ-bonds. I thought it might be fun to look at the stereoelectronic interactions set up in this little system.

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Autoionization of hydrogen fluoride.

Sunday, April 24th, 2016

The autoionization of water involves two molecules transfering a proton to give hydronium hydroxide, a process for which the free energy of reaction is well known. Here I ask what might happen with the next element along in the periodic table, F.

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Deuteronium deuteroxide. The why of pD 7.435.

Friday, April 22nd, 2016

Earlier, I constructed a possible model of hydronium hydroxide, or H3O+.OH– One way of assessing the quality of the model is to calculate the free energy difference between it and two normal water molecules and compare the result to the measured difference. Here I apply a further test of the model using isotopes.

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