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On the Preparation and Reactivity of New Group 15 Biradicaloids

On the Preparation and Reactivity of New Group 15 Biradicaloids. Alexander Hinz (AK Schulz) Universität Rostock 17.03.2013. Outline. Biradicaloids Objective Synthetic Approach Properties Reactivity. Alexander Hinz, Universität Rostock. Biradicaloids. Introduction Organic Biradicals.

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On the Preparation and Reactivity of New Group 15 Biradicaloids

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  1. On thePreparationandReactivityof New Group 15 Biradicaloids Alexander Hinz (AK Schulz) Universität Rostock 17.03.2013

  2. Outline • Biradicaloids • Objective • Synthetic Approach • Properties • Reactivity Alexander Hinz, Universität Rostock Biradicaloids

  3. IntroductionOrganicBiradicals delocalized (non-Kekulémolecules) localized twistedethylene (01) F. Breher, Coord. Chem. Rev.2007, 1007 Alexander Hinz, Universität Rostock Biradicaloids

  4. IntroductionExamplesforKnownHeterocyclobutanediyls Niecke, 1995 Bertrand, 2002 Power, 2004 Lappert, 2004 Schnöckel, 2009 Power, 2009 So, 2012 Sekiguchi, 2011 (02) E. Niecke, A. Fuchs, F. Baumeister, M. Nieger, W. W. Schoeller, Angew. Chem.1995, 640 (03) D. Scheschkewitz, H. Amii, H. Gornitzka, W. W. Schoeller, D. Bourissou, G. Bertrand, Science 2002, 1880 (04) H. Cox, P. B. Hitchcock, M. F. Lappert, L. J.-M. Pierssens, Angew. Chem. 2004, 4600 (05) C. Cui, M. Brynda, M. M. Olmstead, P. P. Power, J. Am. Chem. Soc. 2004, 6510 (06) P. Henke, T. Pankewitz, W. Klopper, F. Breher, H. Schnöckel, Angew. Chem. Int. Ed. 2009, 8141 (07) X. Wang, Y. Peng, M. M. Olmstead, J. C. Fettinger, P. P. Power, J. Am. Chem. Soc. 2009, 14164 (08) K. Takeuchi, M. Ichinohe, A. Sekiguchi, J. Am. Chem. Soc. 2011, 12478 (09) S.-H. Zhang, H.-W. Xi, K. H. Lim, Q. Meng, M.-B. Huang, C.-W. So, Chem. Eur. J. 2012, 4258 Alexander Hinz, Universität Rostock Biradicaloids

  5. Synthetic Approach reductionof 1,3-dichloro-cyclo-1,3-diphospha-2,4-diazanes R = bulkygroup redA = reducingagent Alexander Hinz, Universität Rostock Biradicaloids

  6. Small StericStrain β-[NPDmp]4 α-[NPtBu]4 β-[NPtBu]4 (10) D. DuBois, E. N. Duesler, R. T. Paine, Chem. Comm. 1984, 448 (11) H. Bladt, S. G. Calera, J. M. Goodman, R. J. Less, C. Naseri, A. Steiner. D. S. Wright, Chem. Comm.2009, 6637 Alexander Hinz, Universität Rostock Biradicaloids

  7. A Labile Biradicaloid: [P(µ-NHyp)]2 δ(31P) = 257 δ(31P) = 334 δ(31P) = 297 (12) T. Beweries, R. Kuzora, U. Rosenthal, A. Schulz, A. Villinger, Angew. Chem. 2011, 8974 Alexander Hinz, Universität Rostock Biradicaloids

  8. A StableBiradicaloid: [P(µ-NTer)]2 redA= [Cp2Ti(btmsa)], [Cp2TiCl]2, Mg, Mg(anthracene) d in Å (12) T. Beweries, R. Kuzora, U. Rosenthal, A. Schulz, A. Villinger, Angew. Chem. 2011, 8974 (13) F. Reiß, A. Schulz, A. Villinger, N. Weding, Dalton Trans.2010, 9962 Alexander Hinz, Universität Rostock Biradicaloids

  9. Calculations S-T-gap = 22.6 kcal/mol NICS(0) = -6 ppm (12) T. Beweries, R. Kuzora, U. Rosenthal, A. Schulz, A. Villinger, Angew. Chem. 2011, 8974 Alexander Hinz, Universität Rostock Biradicaloids

  10. [P(µ-NTer)]2 and[As(µ-NTer)]2 molar magneticsusceptibility of [P(µ-NTer)]2 d in Å (14) S. Demeshko, C. Godemann, R. Kuzora, A. Schulz, A. Villinger, Angew. Chem. 2013, 2159 Alexander Hinz, Universität Rostock Biradicaloids

  11. Oxidation withSilverSalts 19F NMR 31P NMR trans-isomer cis-isomer cis-isomer trans-isomer δ(31P) = 250 (trans), 203 (cis) δ(19F) = -32.3 (cis), -33.5 (trans) J in Hz Alexander Hinz, Universität Rostock Biradicaloids

  12. Addition of Small MoleculesAlkyne Σrcov As-As = 2.42 As-N = 1.92 As-C = 1.96 P-P = 2.22 P-N = 1.82 P-C = 1.86 C-C = 1.50 C=C = 1.34 C≡C = 1.20 As-As = 2.750 As-C1 = 2.039 C1-C1‘ = 1.342 δ(31P) = 259 P1-P1‘ = 2.520 P1-C1 = 1.915 C1-C1‘ = 1.349 d in Å Alexander Hinz, Universität Rostock Biradicaloids

  13. Addition of Small MoleculesCarbodiimides Σ(<C110) = 360° Σ(<N7) = 360° Σrcov P-P = 2.22 P-N = 1.82 P-C = 1.86 C-N = 1.46 C=N = 1.27 C≡N = 1.14 C-C = 1.50 C=C = 1.34 P3-P4 = 2.513 P3-N7 = 1.764 P4-C110 = 1.941 C110-N7 = 1.388 C110-N8 = 1.280 δ(31P) = 232, 210 [d, 2J(P,P) = 6 Hz] d in Å Alexander Hinz, Universität Rostock Biradicaloids

  14. Addition of Small MoleculesDiazene Σrcov As-As = 2.42 As-N = 1.92 As-C = 1.96 P-P = 2.22 P-N = 1.82 P-C = 1.86 N-N = 1.42 N=N = 1.20 P1-P2 = 2.496 P1-N3 = 1.756 P2-N4 = 1.765 N3-N4 = 1.453 As1-As2 = 2.734 As1-N3 = 1.865 As2-N4 = 1.864 N3-N4 = 1.445 δ(31P) = 204 d in Å Alexander Hinz, Universität Rostock Biradicaloids

  15. Trapping – The Other Way Round Σrcov P-P = 2.22 P-N = 1.82 P-C = 1.86 d in Å Alexander Hinz, Universität Rostock Biradicaloids

  16. Trapping – The Other Way Round AA‘XX‘ pattern, 10 lines δ(P1, P2) = 273.4 δ(P3, P4) = -9.4 = (PhP)6 I = 0.255, x = 5.9% Alexander Hinz, Universität Rostock Biradicaloids

  17. Trapping – The Other Way Round δ(P1, P2) = 273.4 δ(P3, P4) = -9.4 δ(P1, P2) = 101.2 δ(P3, P4) = -1.7 bicyclo-[1.1.2]diazatetraphosphane cyclo-azatetraphosphane J in Hz (15) M. Baudler, P. Lütkecosmann, Z. anorg. allg. Chem. 1981, 38 Alexander Hinz, Universität Rostock Biradicaloids

  18. Rearrangement – An Azaphosphiridine δ(31P) = 245 δ(31P) = -43.0, -65.6 1J(P-P) = -114 Hz compareswellwithNiecke‘sazaphosphiridines (16) W. W. Seidel, M. J. Meel, M. Schaffrath, T. Pape, Eur. J. Inorg. Chem. 2007, 3526 (17) E. Niecke, R. Rüger, W. W. Schoeller, Angew. Chem.1981, 1110 Alexander Hinz, Universität Rostock Biradicaloids

  19. Rearrangement – An Azaphosphiridine different behaviourof [P(µ-NTer)]2and[As(µ-NTer)]2 Σrcov As-As = 2.42 As-N = 1.92 As-C = 1.96 C=C = 1.34 As1-As2 = 2.767 As1-C49 = 2.041 As2-C50 = 2.006 C49-C50 = 1.347 d in Å (18) D. Barion, C. Gärtner-Winkhaus, M. Link, M. Nieger, E. Niecke, Chem. Ber. 1993, 2187 Alexander Hinz, Universität Rostock Biradicaloids

  20. A SimilarRearrangement Burford, 1999 Σrcov P-P = 2.22 P-N = 1.82 P-C = 1.86 C-N = 1.46 C=N = 1.27 C-C =1.50 C=C = 1.34 C-S = 1.78 angle betweenthe planes 104° vs 98° d in Å (19) N. Burford, D. J. LeBlanc, Inorg. Chem.1999, 2248 Alexander Hinz, Universität Rostock Biradicaloids

  21. SummaryNew Main Group Element Cage Molecules Alexander Hinz, Universität Rostock Biradicaloids

  22. Acknowledgements • Prof. Axel Schulz • Dr. Alexander Villinger • Prof. Wolfram W. Seidel • Prof. Uwe Rosenthal • Dipl. Chem. Christian Hering • Dipl. Chem. René Kuzora • Dipl. Chem. Christian Godemann • DFG – Funding Thankyouforyourattention. Alexander Hinz, Universität Rostock Biradicaloids

  23. [P(µ-NTer]2Reactions δ(31P) = 285, 18 (2J(P,P) = 13 Hz) δ(31P) = 228 δ(31P) = 284, 248 (2J(P,P) = 29 Hz) δ(31P) = 229, 199 (2J(P,P) = 13 Hz) δ(31P) = 288, 206 (2J(P,P) = 23 Hz) δ(31P) = 220, 201 (2J(P,P) = 12 Hz) Alexander Hinz, Universität Rostock Biradicaloids

  24. Element ActivationChalcogens d in Å Alexander Hinz, Universität Rostock Biradicaloids

  25. [As(µ-NTer]2Reactions Alexander Hinz, Universität Rostock Biradicaloids

  26. (19) R. Riedel, H.-D. Hausen, E. Fluck, Angew. Chem. 1985, 1050 Alexander Hinz, Universität Rostock Biradicaloids

  27. 31P-NMR: +90 °C to -80 °C Alexander Hinz, Universität Rostock Biradicaloids

  28. [P(µ-NTer]2Reactions δ(31P) = 262, 229 δ(31P) = 250, 203 δ(31P) = 237 δ(31P) = 310, 281 Alexander Hinz, Universität Rostock Biradicaloids

  29. Sband Bi Alexander Hinz, Universität Rostock Biradicaloids

  30. Allylic NPN-System (11) P. B. Hitchcock, H. A. Jasim, M. F. Lappert, H. D. Williams, Chem. Comm. 1986, 1634 (12) E. Niecke, R. Detsch, M. Nieger, W. W. Schoeller, Chem. Ber. 1992, 1119 Alexander Hinz, Universität Rostock Biradicaloids

  31. Hyp + Mg Alexander Hinz, Universität Rostock Biradicaloids

  32. Oxidation withSilverSalts trans-isomer only! δ(31P) = 243 (cm) Alexander Hinz, Universität Rostock Biradicaloids

  33. Oxidation withSilverSalts 19F NMR 31P NMR trans-isomer cis-isomer cis-isomer trans-isomer 1J(P-F) = -1209 2J(P-P) = 59.0 3J(P-F) = 13.2 4J(F-F) = 7.39 1J(P-F) = -1227 2J(P-P) = 57.1 3J(P-F) = 38.6 4J(F-F) = 35.1 δ(19F) = -32.3 (cis), -33.5 (trans) J in Hz Alexander Hinz, Universität Rostock Biradicaloids

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