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Prediction of a New Delocalised Bonding Motif between Group 15 or Group 16 Atoms

2011; Wiley; Volume: 12; Issue: 13 Linguagem: Inglês

10.1002/cphc.201100423

1439-7641

Michæl Bühl, Petr Kilián, J. Derek Woollins,

Asymmetric Synthesis and Catalysis

ChemPhysChemVolume 12, Issue 13 p. 2405-2408 Communication Prediction of a New Delocalised Bonding Motif between Group 15 or Group 16 Atoms Prof. Dr. Michael Bühl, Corresponding Author Prof. Dr. Michael Bühl [email protected] School of Chemistry, University of St. Andrews, North Haugh, St. Andrews, Fife KY16 9ST (UK), Fax: (+44) 1334-463-808School of Chemistry, University of St. Andrews, North Haugh, St. Andrews, Fife KY16 9ST (UK), Fax: (+44) 1334-463-808Search for more papers by this authorDr. Petr Kilian, Dr. Petr Kilian School of Chemistry, University of St. Andrews, North Haugh, St. Andrews, Fife KY16 9ST (UK), Fax: (+44) 1334-463-808Search for more papers by this authorProf. Dr. J. Derek Woollins, Prof. Dr. J. Derek Woollins School of Chemistry, University of St. Andrews, North Haugh, St. Andrews, Fife KY16 9ST (UK), Fax: (+44) 1334-463-808Search for more papers by this author Prof. Dr. Michael Bühl, Corresponding Author Prof. Dr. Michael Bühl [email protected] School of Chemistry, University of St. Andrews, North Haugh, St. Andrews, Fife KY16 9ST (UK), Fax: (+44) 1334-463-808School of Chemistry, University of St. Andrews, North Haugh, St. Andrews, Fife KY16 9ST (UK), Fax: (+44) 1334-463-808Search for more papers by this authorDr. Petr Kilian, Dr. Petr Kilian School of Chemistry, University of St. Andrews, North Haugh, St. Andrews, Fife KY16 9ST (UK), Fax: (+44) 1334-463-808Search for more papers by this authorProf. Dr. J. Derek Woollins, Prof. Dr. J. Derek Woollins School of Chemistry, University of St. Andrews, North Haugh, St. Andrews, Fife KY16 9ST (UK), Fax: (+44) 1334-463-808Search for more papers by this author First published: 08 July 2011 https://doi.org/10.1002/cphc.201100423Citations: 21Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onEmailFacebookTwitterLinkedInRedditWechat Graphical Abstract Fixed bonds: Using suitably constrained molecular scaffolds, electron delocalisation over four centers can be enforced in X-E-E-X moieties (where E=group 15 or 16 element, X=acceptor, see picture). Identified through DFT calculations, a new facet of chemical bonding is waiting to be discovered. Supporting Information Detailed facts of importance to specialist readers are published as "Supporting Information". Such documents are peer-reviewed, but not copy-edited or typeset. They are made available as submitted by the authors. Filename Description cphc_201100423_sm_miscellaneous_information.pdf534.7 KB miscellaneous_information Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article. References 1P. Ball, Nature 2011, 469, 26. 2For example: 2aS. Alvarez, R. Hoffmann, C. Mealli, Chem. Eur. J. 2009, 15, 8358; 2bH. S. Rzepa, Nat. Chem. 2009, 1, 510. 3 3aP. Kilian, F. R. Knight, J. D. Woollins, Chem. Eur. J. 2011, 17, 2302; 3bP. Kilian, F. R. Knight, J. D. Woollins, Coord. Chem. Rev. 2011, 255, 1387. 4K. Wiberg, Tetrahedron 1968, 24, 1083. 5 5aR. W. F. Bader, Atoms in Molecules, Oxford Press, New York, 1990; 5b The Quantum Theory of Atoms in Molecules (Eds.: ), Wiley-VCH, Weinheim, 2007. 6P. Kilian, A. M. Z. Slawin, J. D. Woollins, Chem. Eur. J. 2003, 9, 215. 7Replacing the SiMe3 groups in 1 with the even stronger donor Li(OMe2)3 affords PP and PCl distances of 2.10 and 2.94 Å, respectively, that is, essentially a PP double bond and dissociation of Cl−. 8W. Malish, W. Angerer, A. H. Cowley, N. C. Norman, J. Chem. Soc. Chem. Commun. 1985, 1811. 9M. Bühl, H. Kabrede, J. Chem. Theory Comput. 2006, 2, 1282. 10These couplings are much larger than, for example, 1J(PP) in the donor–acceptor complex Me3P-PF5, +717 Hz (which is well-reproduced at the present DFT level and at comparable ones, see: M. A. M. Forgeron, M. Gee, R. E. Wasylishen, J. Phys. Chem. A 2004, 108, 4895). 11E. Horn, T. Nakahodo, N. Fukurawa, Z. Kristallogr—New Cryst. Struct. 2000, 215, 23; for this molecule, a SeSe WBI of 0.55 is obtained (B3LYP: F. R. Knight, A. L. Fuller, M. Bühl, A. M. Z. Slawin, J. D. Woollins, Chem. Eur. J. 2010, 16, 7503), suggesting a high 3c4e character. 12E.g.: 12aW. B. Schweizer, G. Procter, M. Kaftory, J. D. Dunitz, Helv. Chim. Acta 1978, 61, 2783; 12bJ. D. Wallis, R. J. C. Easton, J. D. Dunitz, Helv. Chim. Acta 1993, 76, 1411. 136 is predicted to be stable against Br2 elimination by 21.6 kcal mol−1. 14E. Faoro, G. M. de Oliveira, E. S. Lang, C. B. Pereira, J. Organomet. Chem. 2010, 695, 1480. Citing Literature Volume12, Issue13September 12, 2011Pages 2405-2408 ReferencesRelatedInformation