Archive for the ‘crystal_structure_mining’ Category
Saturday, May 8th, 2021
Following from much discussion over the last decade about the nature of C2, a diatomic molecule which some have suggested sustains a quadruple bond between the two carbon atoms, new ideas are now appearing for molecules in which such a bond may also exist between carbon and a transition metal atom. A suggested, albeit hypothetical example was C⩸Fe(CO)3[1]. Iron has a [Ar].3d6.4s2 electronic configuration and if we ionise to balance a C4- ligand, the iron becomes formally FeVI or [Ar].3d4. By adding 14 electrons deriving from the seven “bonds” to the 3d4, including a quadruple count from carbon, the Fe formally completes its 18-electron valence shell, as also found in e.g. Ferrocene.
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References
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A.J. Kalita, S.S. Rohman, C. Kashyap, S.S. Ullah, and A.K. Guha, "Transition metal carbon quadruple bond: viability through single electron transmutation", Physical Chemistry Chemical Physics, vol. 22, pp. 24178-24180, 2020. http://dx.doi.org/10.1039/d0cp03436c
Tags:Interesting chemistry
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Wednesday, January 20th, 2021
The quote of the post title comes from R. B. Woodward explaining the genesis of the discovery of what are now known as the Woodward-Hoffmann rules for pericyclic reactions.[1] I first wrote about this in 2012, noting that “for (that) blog, I do not want to investigate the transition states”. Here I take a closer look at this aspect.
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References
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R.B. Woodward, and R. Hoffmann, "Stereochemistry of Electrocyclic Reactions", Journal of the American Chemical Society, vol. 87, pp. 395-397, 1965. http://dx.doi.org/10.1021/ja01080a054
Tags:Historical, Interesting chemistry, pericyclic
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Wednesday, May 27th, 2020
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. One of these is an analysis I did in 2012 of Robinson’s original curly arrow illustration.[1] That and the fact that I am about to give a lecture on what I call my autobiographical journey discovering them, to our own students here (remotely of course), has prompted me to revisit my original discussion.
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References
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"Forthcoming events", Journal of the Society of Chemical Industry, vol. 43, pp. 1295-1298, 1924. http://dx.doi.org/10.1002/jctb.5000435208
Posted in crystal_structure_mining, Curly arrows | 1 Comment »
Monday, May 25th, 2020
My previous two posts on the topic of strongest bonds have involved mono and diprotonating N2 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. But how about a metal M+ instead of H+? It turns out that structures containing the fragment Ru-N≡N-Ru are a small but well studied class of organometallic. Here is a search of the CSD crystal database for this motif.
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Sunday, April 19th, 2020
In the news this week is a report of a molecule whose crystal lattice is capable of both storing and releasing large amounts of hydrogen gas at modest pressures and temperatures. Thus “NU-1501-Al” can absorb 14 weight% of hydrogen. To power a low-polluting car with a 500 km range, about 4-5 kg of hydrogen gas would be need to be stored and released safely. The molecule is of interest since it opens a systematic strategy of synthetically driven optimisation towards a viable ultra-porous storage material,[1] much like a lead drug compound can be optimised.
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References
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Z. Chen, P. Li, R. Anderson, X. Wang, X. Zhang, L. Robison, L.R. Redfern, S. Moribe, T. Islamoglu, D.A. Gómez-Gualdrón, T. Yildirim, J.F. Stoddart, and O.K. Farha, "Balancing volumetric and gravimetric uptake in highly porous materials for clean energy", Science, vol. 368, pp. 297-303, 2020. http://dx.doi.org/10.1126/science.aaz8881
Tags:Interesting chemistry
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Monday, April 13th, 2020
A reaction can be thought of as molecular dancers performing moves. A choreographer is needed to organise the performance into the ballet that is a reaction mechanism. Here I explore another facet of the Michael addition of a nucleophile to a conjugated carbonyl compound. The performers this time are p-toluene thiol playing the role of nucleophile, adding to but-2-enal (green) acting as the electrophile and with either water or ammonia serving the role of a catalytic base to help things along.†
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Thursday, January 23rd, 2020
Here is another selection from the Molecules-of-the-Year shortlist published by C&E News, in which hexagonal planar transition metal coordination is identified. This was a mode of metal coordination first mooted more than 100 years ago,[1] but with the first examples only being discovered recently. The C&E News example comprises a central palladium atom surrounded by three hydride and three magnesium atoms, all seven atoms being in the same plane.
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References
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M. Garçon, C. Bakewell, G.A. Sackman, A.J.P. White, R.I. Cooper, A.J. Edwards, and M.R. Crimmin, "A hexagonal planar transition-metal complex", Nature, vol. 574, pp. 390-393, 2019. http://dx.doi.org/10.1038/s41586-019-1616-2
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Saturday, December 28th, 2019
Having shown that carbon as a carbene centre, C: can act as a hydrogen bond acceptor, as seen from a search of crystal structures, I began to wonder if there is any chance that carbon as a radical centre, C• could do so as well. Definitely a subversive thought, since radical centres are supposed to abstract hydrogens rather than to hydrogen bond to them.
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Tags:Interesting chemistry
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Friday, July 19th, 2019
I have previously looked at the topic of hydrogen bonding interactions from the hydrogen of chloroform Here I generalize C-H…O interactions by conducting searches of the CSD (Cambridge structure database) as a function of the carbon hybridisation. I am going to jump straight to a specific molecule XEVJIR (DOI: 10.5517/cc5fgpq) identified from the searches appended to this post as interesting for further inspection.[1]
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References
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K.S. Huang, M.J. Haddadin, M.M. Olmstead, and M.J. Kurth, "Synthesis and Reactions of Some Heterocyclic Azacyanines1", The Journal of Organic Chemistry, vol. 66, pp. 1310-1315, 2001. http://dx.doi.org/10.1021/jo001484k
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