The following is a short question in a problem sheet associated with introductory organic chemistry.
Archive for the ‘Interesting chemistry’ Category
Multiple personalities of Magnesium.
Tuesday, November 5th, 2013The world ash tree of the computer hardware industry… crystalline silicon from 1854.
Thursday, October 31st, 2013The element silicon best represents the digital era of the mid 20th century to the present; without its crystalline form, there would be no computers (or this blog). Although it was first prepared in pure amorphous (powder) form around 1823[1] by Berzelius, it was not until 1854 that Henri Sainte-Claire Deville made it in crystalline form, using metallic aluminium to isolate it. He described it [1] as having a “metallic luster”.
References
Six vs ten aromatic electrons?
Sunday, October 20th, 2013Homoaromaticity is a special case of aromaticity in which π-conjugation is interrupted by a single sp3 hybridized carbon atom (it is sometimes referred to as a suspended π-bond with no underlying σ-foundation). But consider the carbene shown below. This example comes from a recently published article[1] which was highlighted on Steve Bachrach’s blog. Here aromaticity has resulted from a slightly different phenomenon, whereby a 4π-electron planar (and hence nominally anti-aromatic) molecule is elevated to aromatic peerage by promoting the two carbene σ-electrons to have π-status.
References
- B. Chen, A.Y. Rogachev, D.A. Hrovat, R. Hoffmann, and W.T. Borden, "How to Make the σ<sup>0</sup>π<sup>2</sup> Singlet the Ground State of Carbenes", Journal of the American Chemical Society, vol. 135, pp. 13954-13964, 2013. https://doi.org/10.1021/ja407116e
A short non-bonding H…H interaction (continued)
Wednesday, October 2nd, 2013This is a continuation of the discussion started on Steve Bachrach’s blog about a molecule with a very short H…H interaction involving two Si-H groups with enforced proximity. It had been inferred from the X-ray structure[1] that the H…H distance was in the region of 1.50Å. It’s that cis-butene all over again! So is that H…H region a bond? Is it attractive or repulsive? Go read Steve’s blog first.
References
- J. Zong, J.T. Mague, and R.A. Pascal, "Exceptional Steric Congestion in an <i>in</i>,<i>in</i>-Bis(hydrosilane)", Journal of the American Chemical Society, vol. 135, pp. 13235-13237, 2013. https://doi.org/10.1021/ja407398w
An example of an extreme gauche effect: FSSF.
Saturday, September 21st, 2013The best known example of the gauche effect is 1,2-difluoroethane, which exhibits a relatively small preference of ~0.5 kcal/mol for this conformer over the anti orientation, which is also a minimum. But FSSF, which I discussed in the previous post, beats this hands down! It also, by the way, must surely be the smallest molecule (only four atoms) which could be theoretically resolved into two enantiomers (possibly at say 273K?).‡
Patterns of behaviour: serendipity in action for enantiomerisation of F-S-S-Cl
Thursday, September 19th, 2013Paul Schleyer sent me an email about a pattern he had spotted, between my post on F3SSF and some work he and Michael Mauksch had done 13 years ago with the intriguing title “Demonstration of Chiral Enantiomerization in a Four-Atom Molecule“.[1] Let me explain the connection, but also to follow-up further on what I discovered in that post and how a new connection evolved.
References
A two-publisher model for the scientific article: narrative+shared data.
Sunday, September 15th, 2013I do go on rather a lot about enabling or hyper-activating[1] data. So do others[2]. Why is sharing data important?
References
- O. Casher, G.K. Chandramohan, M.J. Hargreaves, C. Leach, P. Murray-Rust, H.S. Rzepa, R. Sayle, and B.J. Whitaker, "Hyperactive molecules and the World-Wide-Web information system", Journal of the Chemical Society, Perkin Transactions 2, pp. 7, 1995. https://doi.org/10.1039/p29950000007
- R. Van Noorden, "Data-sharing: Everything on display", Nature, vol. 500, pp. 243-245, 2013. https://doi.org/10.1038/nj7461-243a
The dimer of SF2: small is beautiful (and weird).
Thursday, September 12th, 2013Andy Extance at the Chemistry World blog has picked up on a fascinating article[1] on the dimer of SF2. This molecule has three F atoms on one S, and only one on the other; FSSF3. But all four S-F bonds are of different length. Lindquist and Dunning claim that the minimum energy pathway to dissociation to two SF2 molecules does not involve breaking either the longest or the weakest SF bond. This was too much for me to resist investigating further!
References
- B.A. Lindquist, and T.H. Dunning, "Bonding in FSSF<sub>3</sub>: Breakdown in Bond Length-Strength Correlations and Implications for SF<sub>2</sub> Dimerization", The Journal of Physical Chemistry Letters, vol. 4, pp. 3139-3143, 2013. https://doi.org/10.1021/jz401578h
Full-colour 3D printing of molecular models and orbitals (wavefunctions).
Sunday, August 18th, 2013We have been experimenting with full-colour 3D printing of molecular objects. I thought I might here share some of our observations. Firstly, I list the software used: