Fluorinated TRISPHAT Anions: Spectroscopic Probes for Detailed Asymmetric Ion Pairing Studies
2005; Wiley; Volume: 44; Issue: 32 Linguagem: Inglês
10.1002/anie.200500862
ISSN1521-3773
AutoresRichard Frantz, André Pinto, Samuel Constant, Gérald Bernardinelli, Jérôme Lacour,
Tópico(s)Radioactive element chemistry and processing
ResumoAngewandte Chemie International EditionVolume 44, Issue 32 p. 5060-5064 Communication Fluorinated TRISPHAT Anions: Spectroscopic Probes for Detailed Asymmetric Ion Pairing Studies† Richard Frantz Dr., Richard Frantz Dr. Department of Organic Chemistry, University of Geneva quai Ernest Ansermet 30, 1211 Genève 4, Switzerland, Fax: (+41) 22-379-3215Search for more papers by this authorAndré Pinto, André Pinto Department of Organic Chemistry, University of Geneva quai Ernest Ansermet 30, 1211 Genève 4, Switzerland, Fax: (+41) 22-379-3215Search for more papers by this authorSamuel Constant, Samuel Constant Department of Organic Chemistry, University of Geneva quai Ernest Ansermet 30, 1211 Genève 4, Switzerland, Fax: (+41) 22-379-3215Search for more papers by this authorGérald Bernardinelli Dr., Gérald Bernardinelli Dr. Laboratory of Crystallography, University of Geneva quai Ernest Ansermet 24, 1211 Genève 4, SwitzerlandSearch for more papers by this authorJérôme Lacour Prof., Jérôme Lacour Prof. [email protected] Department of Organic Chemistry, University of Geneva quai Ernest Ansermet 30, 1211 Genève 4, Switzerland, Fax: (+41) 22-379-3215Search for more papers by this author Richard Frantz Dr., Richard Frantz Dr. Department of Organic Chemistry, University of Geneva quai Ernest Ansermet 30, 1211 Genève 4, Switzerland, Fax: (+41) 22-379-3215Search for more papers by this authorAndré Pinto, André Pinto Department of Organic Chemistry, University of Geneva quai Ernest Ansermet 30, 1211 Genève 4, Switzerland, Fax: (+41) 22-379-3215Search for more papers by this authorSamuel Constant, Samuel Constant Department of Organic Chemistry, University of Geneva quai Ernest Ansermet 30, 1211 Genève 4, Switzerland, Fax: (+41) 22-379-3215Search for more papers by this authorGérald Bernardinelli Dr., Gérald Bernardinelli Dr. Laboratory of Crystallography, University of Geneva quai Ernest Ansermet 24, 1211 Genève 4, SwitzerlandSearch for more papers by this authorJérôme Lacour Prof., Jérôme Lacour Prof. [email protected] Department of Organic Chemistry, University of Geneva quai Ernest Ansermet 30, 1211 Genève 4, Switzerland, Fax: (+41) 22-379-3215Search for more papers by this author First published: 08 August 2005 https://doi.org/10.1002/anie.200500862Citations: 26 † We thank Prof. Ian Dance for helpful discussions and preliminary calculations and Prof. Alceo Macchioni for his expert advice on HOESY NMR experiments. We are grateful for financial support of this work by the Swiss National Science Foundation, the Federal Office for Education and Science, and the Sandoz Family Foundation (R.F., J.L.). Read 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 Placing fluorine atoms at selected positions allows enantiopure hexacoordinate phosphate anions to behave as effective chiral solvating and resolving agents for RuII complexes (the structure of one of the anions is shown: F: yellow; O: red; Cl: green; P: purple). The structural features of the asymmetric ion pairing can be determined by NMR spectroscopy owing to the presence of the fluorine atoms. Supporting Information Supporting information for this article is available on the WWW under http://www.wiley-vch.de/contents/jc_2002/2005/z500862_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. References 1M. 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Zuccaccia, J. Organomet. Chem. 2004, 689, 647–661; E. Martinez-Viviente, P. S. Pregosin, L. Vial, C. Herse, J. Lacour, Chem. Eur. J. 2004, 10, 2912–2918; C. Zuccaccia, N. G. Stahl, A. Macchioni, M. C. Chen, J. A. Roberts, T. J. Marks, J. Am. Chem. Soc. 2004, 126, 1448–1464; J. M. Goicoechea, M. F. Mahon, M. K. Whittlesey, P. G. A. Kumar, P. S. Pregosin, Dalton Trans. 2005, 588–597. 8BArF=tetrakis(3,5-bistrifluoromethylphenyl)borate. 9 9aJ. Lacour, C. Ginglinger, C. Grivet, G. Bernardinelli, Angew. Chem. 1997, 109, 660–662; Angew. Chem. Int. Ed. Engl. 1997, 36, 608–609; 9bJ. Lacour, V. Hebbe-Viton, Chem. Soc. Rev. 2003, 32, 373–382; 9cJ. Lacour, R. Frantz, Org. Biomol. Chem. 2005, 3, 15–19. 10 10aJ. Lacour, J. J. Jodry, C. Ginglinger, S. Torche-Haldimann, Angew. Chem. 1998, 110, 2522–2524; Angew. Chem. Int. Ed. 1998, 37, 2379–2380; 10bJ. Lacour, C. Goujon-Ginglinger, S. Torche-Haldimann, J. J. Jodry, Angew. Chem. 2000, 112, 3830–3832; Angew. Chem. Int. Ed. 2000, 39, 3695–3697; 10cD. Monchaud, J. J. Jodry, D. Pomeranc, V. Heitz, J. C. Chambron, J. P. Sauvage, J. Lacour, D. Monchaud, Angew. Chem. 2002, 114, 2423–2425; Angew. Chem. Int. Ed. 2002, 41, 2317–2319; 10dC. Herse, D. Bas, F. C. Krebs, T. Bürgi, J. Weber, T. Wesolowski, B. W. Laursen, J. Lacour, Angew. Chem. 2003, 115, 3270–3274; Angew. Chem. Int. Ed. 2003, 42, 3162–3166. 11O. Maury, J. Lacour, H. Le Bozec, Eur. J. Inorg. Chem. 2001, 201–204. 12C. Pérollier, S. Constant, J. J. Jodry, G. Bernardinelli, J. Lacour, Chem. Commun. 2003, 2014–2015. 13Crystal data: The cell dimensions and intensities were measured at 200 K on a Stoe IPDS diffractometer with graphite-monochromated MoKα radiation (λ=0.71073 Å). (−)-[5][Δ-4 a] (C18H3O6FPCl8)−(C26H29N2O)+(C3H6O): Mr=1092.4; orthorhombic space group, P212121, a=11.5311(5), b=19.2565(10), c=22.6497(13) Å; V=5029.3(4) Å3, Z=4, μ=0.537 mm−1, ρcalcd=1.443 g cm−3. Of 70 173 measured reflections, 10 859 were unique and 4837 were observed (|Fo|>4σ (Fo)); R=0.039, ωR=0.035, Flack parameter x=−0.03(8). (−)-[5][Δ-4 b] (C18H3O6FPCl8)−(C26H29N2O)+(C3H6O): Mr=1092.4; orthorhombic space group, P212121, a=11.3676(5), b=19.0586(11), c=22.9182(12) Å; V=4965.2(4) Å3, Z=4, μ=0.544 mm−1, ρcalcd=1.461 g cm−3. Of 69474 measured reflections, 10 668 were unique and 5449 were observed (|Fo|>4σ (Fo)); R=0.036, ωR=0.035, Flack parameter x=−0.03(8), the fluorine atom is disordered on the C4 and C5 positions with refined population parameters of 0.70(1) and 0.30(1) respectively. CCDC-265389 and CCDC-265390 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge from the Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif. 14Circular dichroism analysis of salts (−)-[5][Δ-4 a] and (−)-[5][Δ-4 b] (MeOH, ≈10−6 M) revealed strong exciton coupling in the π–π* region with positive and negative Cotton effects at lowest and highest wavelengths, confirming the Δ configuration: D. Bas, T. Bürgi, J. Lacour, J. Vachon, J. Weber, Chirality 2005, 15, S143–S145. 15D. Monchaud, J. Lacour, C. Coudret, S. Fraysse, J. Organomet. Chem. 2001, 624, 388–391. 16A. J. McCaffery, S. F. Mason, J. Norman, J. Chem. Soc. A 1969, 1428–1441; R. Kuroda, Y. Saito in Circular Dichroism: Principles and Applications (Eds.: ), Wiley, New York, 1994, pp. 217–258; M. Ziegler, A. von Zelewsky, Coord. Chem. Rev. 1998, 177, 257–300. 17D. Drago, P. S. Pregosin, A. Pfaltz, Chem. Commun. 2002, 286–287; N. C. Fletcher, F. R. Keene, J. Chem. Soc. Dalton Trans. 1999, 683–689; A. Macchioni, G. Bellachioma, G. Cardaci, M. Travaglia, C. Zuccaccia, B. Milani, G. Corso, E. Zangrando, G. Mestroni, C. Carfagna, M. Formica, Organometallics 1999, 18, 3061–3069. 18I. Dance, CrystEngComm 2003, 5, 208–221. 19T. Steiner, G. R. Desiraju, Chem. Commun. 1998, 891–892; F. Grepioni, G. Cojazzi, S. M. Draper, N. Scully, D. Braga, Organometallics 1998, 17, 296–307. 20The 1H,19F-HOESY measurements were carried out on a 500-MHz Bruker DRX spectrometer equipped with a QNP probe; mixing time 700 ms, sample concentration 5 mM, number of scans 96, number of increments in the F1 dimension 256. 21The 1H,19F-HOESY NMR experiment on salt [rac-2](PF6)2 shows cross-peaks of the achiral anions with all the protons of the coordination complex (see the Supporting Information). 22The DFT calculations on the preferred geometry of interaction between ions Δ-1 and Δ-2 clearly showed this preferred topography. I. Dance, unpublished results. 23Anions 4 a and 4 b also possess H nuclei on the fluorine-containing ligands, which can be equally used for detecting interionic contacts. The results of the 1H,1H-NOESY experiments on salts [Δ-2][Δ-4 a]2 and [Δ-2][Δ-4 b]2 are reported in the Supporting Information and confirm the data from the HOESY experiments. These experiments further show that the preferred interaction of the anion with the cation comes indeed from the face containing the fluorine substituent. Citing Literature Volume44, Issue32August 12, 2005Pages 5060-5064 ReferencesRelatedInformation
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