Posts Tagged ‘pence’
Wednesday, March 12th, 2014
My previous post related to the aromatic electrophilic substitution of benzene using as electrophile phenyl diazonium chloride. Another prototypical reaction, and again one where benzene is too inactive for the reaction to occur easily, is the catalyst-free bromination of benzene to give bromobenzene and HBr.
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Tags:activation energy, animation, aromatic, Boris Galabov, co-author, electrophilic, Interesting chemistry, lowest energy solution, o/p director of aromatic electrophilic substitution, Paul Schleyer, pence, substitution
Posted in reaction mechanism | 7 Comments »
Saturday, November 23rd, 2013
Mercury (IV) tetrafluoride attracted much interest when it was reported in 2007[1] as the first instance of the metal being induced to act as a proper transition element (utilising d-electrons for bonding) rather than a post-transition main group metal (utilising just s-electrons) for which the HgF2 dihalide would be more normal (“Is mercury now a transition element?”[2]). Perhaps this is the modern equivalent of transmutation! Well, now we have new speculation about how to induce the same sort of behaviour for caesium; might it form CsF3 (at high pressures) rather than the CsF we would be more familiar with.[3] Here I report some further calculations inspired by this report.
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References
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X. Wang, L. Andrews, S. Riedel, and M. Kaupp, "Mercury Is a Transition Metal: The First Experimental Evidence for HgF4", Angewandte Chemie International Edition, vol. 46, pp. 8371-8375, 2007. http://dx.doi.org/10.1002/anie.200703710
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M. Miao, "Caesium in high oxidation states and as a p-block element", Nature Chemistry, vol. 5, pp. 846-852, 2013. http://dx.doi.org/10.1038/nchem.1754
Tags:animation, energy, free energy barrier, free energy change, Hypervalency, Interesting chemistry, metal, pence, post-transition main group metal, potential energy surface
Posted in Uncategorised | 13 Comments »
Friday, July 5th, 2013
A comment made on the previous post on the topic of hexa-coordinate carbon cited an article entitled “Observation of hypervalent CLi6 by Knudsen-effusion mass spectrometry“[1] by Kudo as a amongst the earliest of evidence that such species can exist (in the gas phase). It was a spectacular vindication of the earlier theoretical prediction[2],[3] that such 6-coordinate species are stable with respect to dissociation to CLi4 and Li2.
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References
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H. Kudo, "Observation of hypervalent CLi6 by Knudsen-effusion mass spectrometry", Nature, vol. 355, pp. 432-434, 1992. http://dx.doi.org/10.1038/355432a0
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E.D. Jemmis, J. Chandrasekhar, E.U. Wuerthwein, P.V.R. Schleyer, J.W. Chinn, F.J. Landro, R.J. Lagow, B. Luke, and J.A. Pople, "Lithiated carbocations. The generation, structure, and stability of CLi5+", Journal of the American Chemical Society, vol. 104, pp. 4275-4276, 1982. http://dx.doi.org/10.1021/ja00379a051
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P.V.R. Schleyer, E.U. Wuerthwein, E. Kaufmann, T. Clark, and J.A. Pople, "Effectively hypervalent molecules. 2. Lithium carbide (CLi5), lithium carbide (CLi6), and the related effectively hypervalent first row molecules, CLi5-nHn and CLi6-nHn", Journal of the American Chemical Society, vol. 105, pp. 5930-5932, 1983. http://dx.doi.org/10.1021/ja00356a045
Tags:energy, gas phase, Hypervalency, Interesting chemistry, Knudsen, low energy 2s/2p carbon, metal-metal bonding, pence
Posted in Uncategorised | 7 Comments »
Monday, May 28th, 2012
Streptomycin is an antibiotic active against tuberculosis, and its discovery has become something of a cause célèbre. It was first isolated on October 19, 1943 by a graduate student Albert Schatz in the laboratory of Selman Waksman at Rutgers University. I want to concentrate in this post on its molecular structure. Its initial isolation was followed by an extraordinarily concentrated period of about three years devoted to identifying that structure, culminating in a review of this chemistry in 1948 by Lemieux and Wolfram.[1] This review presents the structure as shown below (left). The modern rendering on the right is based on a crystal structure done in 1978.[2]‡
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References
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R. Lemieux, and M. Wolfrom, "The Chemistry of Streptomycin", Advances in Carbohydrate Chemistry, pp. 337-384, 1948. http://dx.doi.org/10.1016/S0096-5332(08)60034-X
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"The crystal and molecular structure of streptomycin oxime selenate tetrahydrate", Proceedings of the Royal Society of London. A. Mathematical and Physical Sciences, vol. 359, pp. 365-388, 1978. http://dx.doi.org/10.1098/rspa.1978.0047
Tags:Albert Schatz, candidate for its formula, Historical, Interesting chemistry, laboratory of Selman Waksman, MS, muse, pence, Rutgers University, tuberculosis, X-ray
Posted in Uncategorised | 1 Comment »
Friday, April 29th, 2011
The two previous posts have explored one of the oldest bonding rules (pre-dating quantum mechanics), which postulated that filled valence shells in atoms forming molecules follow the magic numbers 2, 8, 18 and 32. Of the 59,025,533 molecules documented at the instant I write this post, only one example is claimed for the 32-electron class. Here I suggest another, Nobelocene (one which given the radioactive instability of nobelium, is unlikely to be ever confirmed experimentally!)
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Tags:Hess, Interesting chemistry, pence
Posted in Uncategorised | 4 Comments »
Monday, April 25th, 2011
In discussing ferrocene in the previous post, I mentioned Irving Langmuir’s 1921 postulate that filled valence shells in what he called complete molecules would have magic numbers of 2, 8, 18 or 32 electrons (deriving from the sum of terms in 2[1+3+5+7]). The first two dominate organic chemistry of course, whilst the third is illustrated by the transition series, ferrocene being an example of such. The fourth case is very much rarer, only one example ever having been suggested[1], it deriving from the actinides. In this post, I thought I would augment ferrocene (an 18-electron example) with beryllocene (an 8-electron example) and then speculate about 32-electron metallocenes.
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References
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J. Dognon, C. Clavaguéra, and P. Pyykkö, "Towards a 32‐Electron Principle: Pu@Pb12 and Related Systems", Angewandte Chemie International Edition, vol. 46, pp. 1427-1430, 2007. http://dx.doi.org/10.1002/anie.200604198
Tags:8-electron rule, beryllocene, Cambridge, Interesting chemistry, Irving Langmuir, metal, pence, uranocene
Posted in Uncategorised | 11 Comments »
Sunday, April 17th, 2011
The structure of ferrocene was famously analysed by Woodward and Wilkinson in 1952[1],[2], symmetrically straddled in history by Pauling (1951) and Watson and Crick (1953). Quite a trio of Nobel-prize winning molecular structural analyses, all based on a large dose of intuition. The structures of both proteins and DNA succumbed to models built from simple Lewis-type molecules with covalent (and hydrogen) bonds; ferrocene is intriguingly similar and yet different. Similar because e.g. carbon via four electron pair bonds. He did not (in 1916) realise that 8 = 2(1 + 3), and that the next in sequence would be 18 = 2(1 + 3 + 5). That would have to wait for quantum mechanics, and of course inorganic chemists now call it the 18-electron rule (for an example of the 32-electron rule, or 2+6+10+14, as first suggested by Langmuir in 1921[3] (see also here[4]).
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References
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G. Wilkinson, M. Rosenblum, M.C. Whiting, and R.B. Woodward, "THE STRUCTURE OF IRON BIS-CYCLOPENTADIENYL", Journal of the American Chemical Society, vol. 74, pp. 2125-2126, 1952. http://dx.doi.org/10.1021/ja01128a527
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G. Wilkinson, "The iron sandwich. A recollection of the first four months", Journal of Organometallic Chemistry, vol. 100, pp. 273-278, 1975. http://dx.doi.org/10.1016/S0022-328X(00)88947-0
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I. Langmuir, "Types of Valence", Science, vol. 54, pp. 59-67, 1921. http://dx.doi.org/10.1126/science.54.1386.59
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J. Dognon, C. Clavaguéra, and P. Pyykkö, "Towards a 32‐Electron Principle: Pu@Pb12 and Related Systems", Angewandte Chemie International Edition, vol. 46, pp. 1427-1430, 2007. http://dx.doi.org/10.1002/anie.200604198
Tags:10.1126, 18-electron rule, 54.1386.59, Ferrocene, Historical, Interesting chemistry, normal solution, pence, Tutorial material, valid search query
Posted in Uncategorised | 8 Comments »
Friday, January 21st, 2011
Much of chemistry is about bonds, but sometimes it can also be about anti-bonds. It is also true that the simplest of molecules can have quite subtle properties. Thus most undergraduate courses in chemistry deal with how to describe the bonding in the diatomics of the first row of the periodic table. Often, only the series C2 to F2 is covered, so as to take into account the paramagnetism of dioxygen, and the triple bonded nature of dinitrogen (but never mentioning the strongest bond in the universe!). Rarely is diberyllium mentioned, and yet by its strangeness, it can also teach us a lot of chemistry.
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Tags:diberyllium, energy, excited state, higher energy, higher energy state, Interesting chemistry, pence, Tutorial material
Posted in Uncategorised | 6 Comments »
Thursday, December 16th, 2010
Do you fancy a story going from simplicity to complexity, if not absurdity, in three easy steps? Read on! The following problem appears in one of our (past) examination questions in introductory organic chemistry. From relatively mundane beginnings, one can rapidly find oneself in very unexpected territory.
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Tags:Henry Rzepa, Hypervalency, Interesting chemistry, Jahn-Teller, pence, TfO, tutor
Posted in Uncategorised | 19 Comments »