Henry Rzepa's Blog

Sandwich compounds are the colloquial term used for molecules where a metal atom such as an iron dication is “sandwiched” between two carbon-based rings as ligands, most commonly cyclopentadienyl anion (the “bread”) as in e.g. Ferrocene – a molecule first discovered in 1951. An “inverted” sandwich is where the carbon ring is itself sandwiched between two metal ions and one such was reported this year [1] containing benzene in the middle with scandium as the metal. The novelty of the subsequent four-electron reduction of the benzene “filler” and its ring opening to a linear hexadiene unit resulted in this being selected as one “molecule of the year” for 2025.

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References

1. L. Zhang, Z. Jiang, C. Zhang, K. Cheng, S. Li, Y. Gao, X. Wang, and J. Chu, "Room Temperature Ring Opening of Benzene by Four-Electron Reduction and Carbonylation", Journal of the American Chemical Society, vol. 147, pp. 25017-25023, 2025. https://doi.org/10.1021/jacs.5c08414

The annual “Molecules of the Year” selections are available for the year 2025. A theme was elemental allotropes and one such was carbon in the form of C₄₈ stabilised by formation of a catenane C₄₈.M3 (M = red ligand below)[1] – it was not possible however to crystallise C₄₈.M3. When “unmasked” by removal of the M ligand, the true allotrope C₄₈ had a solution half-life of about 1 hour at 20°C. This follows the reports from 2019 onwards of a series of smaller cyclo[n]carbon allotropes, (n=6,10,12,13,14,16,18,20,26)[2],[3] which were only characterised on a solid surface and not in solution.

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References

1. Y. Gao, P. Gupta, I. Rončević, C. Mycroft, P.J. Gates, A.W. Parker, and H.L. Anderson, "Solution-phase stabilization of a cyclocarbon by catenane formation", Science, vol. 389, pp. 708-710, 2025. https://doi.org/10.1126/science.ady6054
2. K. Kaiser, L.M. Scriven, F. Schulz, P. Gawel, L. Gross, and H.L. Anderson, "An sp-hybridized molecular carbon allotrope, cyclo[18]carbon", Science, vol. 365, pp. 1299-1301, 2019. https://doi.org/10.1126/science.aay1914
3. H. Rzepa, "Cyclo[18]carbon: The Kekulé vibration calculated and hence a mystery!", 2019. https://doi.org/10.59350/jdy16-7rv58

In the previous post,[1] I was commenting that the transition state for borohydride reduction of a ketone contained some close contacts between the hydrogen of the borohydride and the hydrogen of water. A systematic search of the CSD reveals a modest number of such contacts have been observed in crystal structures (Table).  Since it is always good to have a reality check for constructed transition states, here I take a look at some of compounds showing the closest H…H contacts in the experimental database of structures.

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References

1. H. Rzepa, "The mechanism of borohydride reductions. Part 2: 4-t-butyl-cyclohexanone – Dispersion induced stereochemistry.", 2025. https://doi.org/10.59350/x5k75-t2m40

In the previous post[1] I mooted the possibility that a high energy form of the dimer of nitric oxide 1 might nonetheless be able to be detected using suitable traps (such as hydrogenation or cycloaddition). However, an interesting alternative is that this species could be trapped by nitric oxide itself. According to [2] in an article entitled “Decomposition of nitric oxide at elevated pressures” the rate of this termolecular reaction 3NO → N₂O + NO₂ are said to obey third order kinetics. One plausible mechanism for this process is shown below.

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References

1. H. Rzepa, "Hydrogenating the even more mysterious N≡N triple bond in a nitric oxide dimer.", 2025. https://doi.org/10.59350/rzepa.29626
2. T. Melia, "Decomposition of nitric oxide at elevated pressures", Journal of Inorganic and Nuclear Chemistry, vol. 27, pp. 95-98, 1965. https://doi.org/10.1016/0022-1902(65)80196-8

Previously[1] I looked at some of the properties of the mysterious dimer of nitric oxide  1 – not the known weak dimer but a higher energy form with a “triple” N≡N bond. This valence bond isomer of the weak dimer was some 24 kcal/mol higher in free energy than the two nitric oxide molecules it would be formed from. An energy decomposition analysis (NEDA) of 1 revealed an interaction energy[2] of +4.5 kcal/mol for the two radical fragments, compared to eg -27 kcal/mol for the equivalent analysis of the N=N double bond in nitrosobenzene dimer[3] So here I take a look at another property of N≡N bonds via their hydrogenation energy (Scheme), mindful that the dinitrogen molecule requires forcing conditions to hydrogenate, in part because of the unfavourable entropy terms (See Wiki and also here^‡ for a calculation of ΔG₂₉₈).

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References

1. H. Rzepa, "The even more mysterious N≡N triple bond in a nitric oxide dimer.", 2025. https://doi.org/10.59350/rzepa.29429
2. H. Rzepa, "N2O2 as strong dimer? bent NEDA 0 1 0 2 0 -2 Total Interaction (E) : 4.520 Wiberg NN bond index 1.0072 NN stretch 2604 cm-1", 2025. https://doi.org/10.14469/hpc/15468
3. H. Rzepa, "Nitrosobenzene dimer NEDA=2, 0,1 0,1 0,1 Total Interaction (E) : -27.564", 2025. https://doi.org/10.14469/hpc/15444

I started adding citations to my blog posts around 2012 using the Kcite plugin.^‡ Rogue Scholar is a service that monitors registered blog sources and adds all sorts of value to the original post, including identifying such citations and creating a list of them.

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Previously, I pondered about the strange N=N double bond in nitrosobenzene dimer[1] as a follow up to commenting on the curly arrow mechanism of the dimerisation.[2] By the same curly arrow method, one can produce the below, showing how the simpler nitric oxide radical could potentially dimerise to a species with a N≡N triple bond!^† This involves a total of six electrons entering the N-N region, and hence raises the question of whether these all move in a single concerted/synchronous bond forming reaction, or whether they might go in (asynchronous) stages. Here are some calculations[3]) which might shed some light on this aspect.

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References

1. H. Rzepa, "The mysterious N=N double bond in nitrosobenzene dimer.", 2025. https://doi.org/10.59350/rzepa.29383
2. H. Rzepa, "Mechanism of the dimerisation of Nitrosobenzene.", 2025. https://doi.org/10.59350/rzepa.28849
3. H. Rzepa, "N2O2 as strong dimer TS as biradical cis, G = -259.785500", 2025. https://doi.org/10.14469/hpc/15483

In the previous post,[1] I introduced the N=N double bond in nitrosobenzene dimer, arguing that even though it was a formal double bond, its bond dissociation energy made it nonetheless a very weak double bond! This was backed up by a technique known as energy decomposition analysis or EDA. Here I use a variant of this method  known as  NEDA to look at some other strained alkenes, including the famously non-existent tetra t-Butyl ethene.

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References

1. H. Rzepa, "The mysterious N=N double bond in nitrosobenzene dimer.", 2025. https://doi.org/10.59350/rzepa.29383

In an earlier blog, I discussed[1] the curly arrows associated with the known dimerisation of nitrosobenzene, and how the N=N double bond (shown in red below) forms in a single concerted process.

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References

1. H. Rzepa, "Mechanism of the dimerisation of Nitrosobenzene.", 2025. https://doi.org/10.59350/rzepa.28849

I thought I was done with exploring anomeric effects in small sulfur rings. However, I then realised that all the systems that I had described had an odd number of atoms and that I had not looked at any even numbered rings. Thus hexasulfur is a smaller (known) ring version of S₈, the latter by far the best known allotrope of this element of course.

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