Title: Relativistic DFT Calculations of Polyoxotungstate <sup>183</sup>W NMR Spectra: Insight into their Solution Structure
Abstract: ChemPhysChemVolume 4, Issue 5 p. 517-519 Short Communication Relativistic DFT Calculations of Polyoxotungstate 183W NMR Spectra: Insight into their Solution Structure Alessandro Bagno Prof., Alessandro Bagno Prof. [email protected] Dipartimento di Chimica Organica, Università di Padova via Marzolo 1, 35131 Padova, Italy, Fax: (+39) 049-827-5239Search for more papers by this authorMarcella Bonchio Dr., Marcella Bonchio Dr. Istituto CNR per la Tecnologia delle Membrane Sezione di Padova, via Marzolo 1, 35131 Padova, ItalySearch for more papers by this authorAndrea Sartorel Dr., Andrea Sartorel Dr. Dipartimento di Chimica Organica, Università di Padova via Marzolo 1, 35131 Padova, Italy, Fax: (+39) 049-827-5239Search for more papers by this authorGianfranco Scorrano Prof., Gianfranco Scorrano Prof. Dipartimento di Chimica Organica, Università di Padova via Marzolo 1, 35131 Padova, Italy, Fax: (+39) 049-827-5239Search for more papers by this author Alessandro Bagno Prof., Alessandro Bagno Prof. [email protected] Dipartimento di Chimica Organica, Università di Padova via Marzolo 1, 35131 Padova, Italy, Fax: (+39) 049-827-5239Search for more papers by this authorMarcella Bonchio Dr., Marcella Bonchio Dr. Istituto CNR per la Tecnologia delle Membrane Sezione di Padova, via Marzolo 1, 35131 Padova, ItalySearch for more papers by this authorAndrea Sartorel Dr., Andrea Sartorel Dr. Dipartimento di Chimica Organica, Università di Padova via Marzolo 1, 35131 Padova, Italy, Fax: (+39) 049-827-5239Search for more papers by this authorGianfranco Scorrano Prof., Gianfranco Scorrano Prof. Dipartimento di Chimica Organica, Università di Padova via Marzolo 1, 35131 Padova, Italy, Fax: (+39) 049-827-5239Search for more papers by this author First published: 09 May 2003 https://doi.org/10.1002/cphc.200300636Citations: 36Read 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 Graphical Abstract Mapping an uncharted territory: The good correlation between experimental and calculated 183W NMR chemical shifts of polyoxotungstates (see picture) may allow the prediction and assignment of the spectra of unstable or unknown species, and also allow the counterion effect to be addressed. References 1 Thematic issue of Polyoxometalates (Ed. C. L. Hill), Chem. Rev. 1998, 98, 1–390. 2 J. F. Kirby, L. C. W. Baker, Inorg. Chem. 1998, 37, 5537– 5543. 3 C. Brevard, R. Schimpf, G. Tourne, C. M. Tourne, J. Am. Chem. Soc. 1983, 105, 7059– 7063. 4 V. A. Grigoriev, D. Cheng, C. L. Hill, I. A. Weinstock, J. Am. Chem. Soc. 2001, 123, 5292– 5307, and references therein. 5 S. Ganapathy, M. Fournier, J. F. Paul, L. Delevoye, M. Guelton, J. P. Amoreux, J. Am. Chem. Soc. 2002, 124, 7821– 7828. 6 R. Acerete, C. F. Hammer, L. C. W. Baker, J. Am. Chem. Soc. 1982, 104, 5384– 5390. 7 N. N. Sveshnikov, M. T. Pope, Inorg. Chem. 2000, 39, 591– 594. 8 J. Canny, A. Teze, R. Thouvenot, G. Herve, Inorg. Chem. 1986, 25, 2114– 2119. 9 T. Helgaker, M. Jaszunski, K. Ruud, Chem. Rev. 1999, 99, 293– 352. 10 A. Bagno, M. Bonchio, Chem. Phys. Lett. 2000, 317, 123– 128. 11 A. Bagno, M. Bonchio, Eur. J. Inorg. Chem. 2002, 1475– 1483. 12 G. te Velde, F. M. Bickelhaupt, E. J. Baerends, Fonseca Guerra, S. J. A. van Gisbergen, J. G. Snijders, T. Ziegler, J. Comput. Chem. 2001, 22, 931– 967. 13 13a G. Schreckenbach, T. Ziegler, J. Phys. Chem. 1995, 99, 606– 611; 13b G. Schreckenbach, T. Ziegler, Int. J. Quantum Chem. 1997, 61, 899– 918; 13c S. K. Wolff, T. Ziegler, J. Chem. Phys. 1998, 109, 895– 905; 13d S. K. Wolff, T. Ziegler, E. van Lenthe, E. J. Baerends, J. Chem. Phys. 1999, 110, 7689– 7698. 14 We employed the Becke 88 exchange plus the Perdew 86 correlation functional (BP).[15] Basis sets are composed of Slater functions designed for ZORA calculations. Basis I: triple-ζ polarized (TZP) for W, Ru, V, Cl, S, and Li; double-ζ polarized (DZP) for P, F, O, C, and H. Basis II is the corresponding frozen-core basis, with core shells defined as: W.4f, Ru.3d, V.3p, Cl.2p, S.2p, P.2p, O.1 s, C.1 s, except Li and H as in Basis I. Relativistic core potentials were generated with the Dirac utility. 15 X. López, C. Bo, J. M. Poblet, J. Am. Chem. Soc. 2002, 124, 12 574– 12 582. 16 A. Rodriguez-Fortea, P. Alemany, T. Ziegler, J. Phys. Chem. A 1999, 103, 8288– 8294. 17 N. Belai, M. Sadakane, M. T. Pope, J. Am. Chem. Soc. 2001, 123, 2087– 2088. 18 The DMSO ligand may present two conformations of Cs symmetry, which differ only by 2 kcal mol−1 in energy. The calculated Ru-S distance is 2.15 Å.[11] Although the results are similar, only the shieldings of the most stable one are presented. 19 A. Bagno, M. Bonchio, A. Sartorel, G. Scorrano, Eur. J. Inorg. Chem. 2000, 17– 20. 20 Performed with the ADF implementation of the COSMO method (Basis I). The ionic radius of Li+ (1.45 Å) was chosen to reproduce the experimental ΔGh (−118.1 kcal mol−1). Citing Literature Supporting Information Supporting information for this article is available on the WWW under http://www.wiley-vch.de/contents/jc_2267/2003/z636_s.pdf or from the author. 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. Volume4, Issue5May 16, 2003Pages 517-519 ReferencesRelatedInformation
Publication Year: 2003
Publication Date: 2003-05-09
Language: en
Type: article
Indexed In: ['crossref', 'pubmed']
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Cited By Count: 39
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