Posts Tagged ‘metal’
Wednesday, April 17th, 2013
This is another in the occasional series of “what a neat molecule”. In this case, more of a “what a neat idea”. The s-triazine below, when coordinated to eg ZnI2, forms what is called a metal-organic-framework, or MOF. A recent article[1] shows how such frameworks can be used to help solve a long-standing problem in structure determination, how to get a crystal structure on a compound that does not crystallise on its own.
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References
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Y. Inokuma, S. Yoshioka, J. Ariyoshi, T. Arai, Y. Hitora, K. Takada, S. Matsunaga, K. Rissanen, and M. Fujita, "X-ray analysis on the nanogram to microgram scale using porous complexes", Nature, vol. 495, pp. 461-466, 2013. http://dx.doi.org/10.1038/nature11990
Tags: chair, marine natural product, metal, radiation, X-ray
Posted in Interesting chemistry | 1 Comment »
Saturday, March 16th, 2013
Functionalisation of a (hetero)aromatic ring by selectively (directedly) removing protons using the metal lithium is a relative mechanistic newcomer, compared to the pantheon of knowledge on aromatic electrophilic substitution. Investigating the mechanism using quantum calculations poses some interesting challenges, ones I have not previously discussed on this blog.
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Tags: carbon-metal bond, lithiation, metal, metal alkyls, metal lithium, pericyclic
Posted in Hypervalency, Interesting chemistry, Reaction Mechanism, Tutorial material | 2 Comments »
Wednesday, January 16th, 2013
If you search e.g. Scifinder for N,O-diphenyl hydroxylamine (RN 24928-98-1) there is just one literature citation, to a 1962 patent. Nothing else; not even a calculation (an increasing proportion of the molecules reported in Chemical Abstracts have now only ever been subjected to calculation, not synthesis). A search of Reaxys also offers only one hit[1] reporting one unsuccessful attempt in 1963 to prepare this compound. Again, nothing else. Yet show this structure to most organic chemists, and I venture to suggest few would immediately predict this (unless they are experts on benzidine rearrangements).‡
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References
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J.R. Cox, and M.F. Dunn, "The chemistry of O,N-diarylhydroxlamines - I", Tetrahedron Letters, vol. 4, pp. 985-989, 1963. http://dx.doi.org/10.1016/S0040-4039(01)90757-9
Tags: energy, metal, pericyclic
Posted in Historical, Interesting chemistry, Reaction Mechanism | 7 Comments »
Friday, January 4th, 2013
Tags: basic search, Cambridge, CF 3, conformational analysis, gauche, metal, search takes, similar
Posted in Interesting chemistry, Tutorial material | 6 Comments »
Monday, December 24th, 2012
tpap[1], as it is affectionately known, is a ruthenium-based oxidant of primary alcohols to aldehydes discovered by Griffith and Ley. Whereas ruthenium tetroxide (RuO4) is a voracious oxidant[2], its radical anion countered by a tetra-propylammonium cation is considered a more moderate animal[3]. In this post, I want to try to use quantum mechanically derived energies as a pathfinder for exploring what might be going on (or a reality-check if you like).
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References
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S.V. Ley, J. Norman, W.P. Griffith, and S.P. Marsden, "
Tetrapropylammonium Perruthenate, Pr
4
N
+
RuO
4
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, TPAP: A Catalytic Oxidant for Organic Synthesis
", Synthesis, vol. 1994, pp. 639-666, 1994. http://dx.doi.org/10.1055/s-1994-25538
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D.G. Lee, U.A. Spitzer, J. Cleland, and M.E. Olson, "The oxidation of cyclobutanol by ruthenium tetroxide and sodium ruthenate", Canadian Journal of Chemistry, vol. 54, pp. 2124-2126, 1976. http://dx.doi.org/10.1139/v76-304
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D.G. Lee, Z. Wang, and W.D. Chandler, "Autocatalysis during the reduction of tetra-n-propylammonium perruthenate by 2-propanol", The Journal of Organic Chemistry, vol. 57, pp. 3276-3277, 1992. http://dx.doi.org/10.1021/jo00038a009
Tags: energy, free energy, low energy elimination, metal, react freq, RuO4+ ethanol, triplet state energy
Posted in Interesting chemistry, Reaction Mechanism, Tutorial material | No Comments »
Sunday, November 4th, 2012
The text books say that cyclohexenone A will react with a Grignard reagent by delivery of an alkyl (anion) to the carbon of the carbonyl (1,2-addition) but if dimethyl lithium cuprate is used, a conjugate 1,4-addition proceeds, to give the product B shown below. The standard explanation is that the alkyl copper is a “soft” nucleophile attacking the soft conjugate carbon, whereas the alkyl magnesium is a “hard” nucleophile attacking the hard carbonyl carbon. Is this the best explanation?
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Tags: metal, simulation
Posted in Reaction Mechanism, Tutorial material | No Comments »
Wednesday, October 17th, 2012
Every once in a while, one encounters a molecule which instantly makes an interesting point. Thus Ruthenium is ten electrons short of completing an 18-electron shell, and it can form a complex with benzene on one face and a ligand known as trimethylenemethane on the other[1].
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References
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G.E. Herberich, and T.P. Spaniol, "Trimethylenemethane complexes of ruthenium via the trimethylenemethane dianion", Journal of the Chemical Society, Chemical Communications, pp. 1457, 1991. http://dx.doi.org/10.1039/c39910001457
Tags: Iron complex, metal, Postscript
Posted in Interesting chemistry | No 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, Irving Langmuir, metal, pence, uranocene
Posted in Interesting chemistry | 5 Comments »
