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Complexes with novel N,P,C-cage ligands from an azaphosphiridine complex

Complexes with novel N,P,C-cage ligands from an azaphosphiridine complex. José Manuel Villalba Franco Research Group of Prof . R. Streubel University of Bonn, Germany EWPC 10 Regensburg 19 th March 2013. Outline. Intro : three-membered rings

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Complexes with novel N,P,C-cage ligands from an azaphosphiridine complex

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  1. Complexes with novel N,P,C-cage ligands from an azaphosphiridine complex José Manuel Villalba Franco Research Group of Prof. R. Streubel University of Bonn, Germany EWPC 10 Regensburg 19thMarch 2013

  2. Outline • Intro: three-memberedrings • Attempts to synthesize azaphosphiridine complexes • Rearrangements of azaphosphiridine complexes • Summary • Outlook

  3. Introduction Three-membered heterocycles [1,2] [3,4] [1] For s3l3-oxaphosphiranes, see: P. A. Bartlett, N. I. Carruthers, B. M. Winter, K. P. Long, J. Org. Chem. 1982, 47, 1284 –1291. [2] Theory: O. Krahe, F. Neese and R. Streubel, Chem. Eur. J., 2009, 15, 2594 – 2601. [3] For 1,2-l3-azaphosphiridines, see: E. Niecke, A. Seyer and D.-A. Wildbredt, Angew. Chem., 1981, 93, 687–688. [4] Theory: A. Espinosa and R. Streubel, Chem. Eur. J., 2011, 17, 3166 – 3178.

  4. Limitationsofsyntheticprotocolsforazaphosphiridines [5] E. Niecke, A. Seyer and D.-A. Wildbredt, Angew. Chem., 1981, 93, 687–688. [6] N. Huy, L. Ricard and F. Mathey, Heteroat. Chem., 1998, 6,597-600. [7] M. Vlaar, P. Valkier,F. Kanter,M. Schakel, A. Ehlers, A. Spek, M. Lutz and K. LammertsmaChem. Eur. J., 2001, 7,3551-3557.

  5. “High“ temperature route: “Low“ temperature route: [8] R. Streubel, A. Ostrowski, H. Wilkens, F. Ruthe, J. Jeske and P. G. Jones, Angew. Chem., Int. Ed. Engl., 1997, 36,378–381. [9] S. Fankel,H. Helten,G. von Frantzius, G. Schnakenburg,J. Daniels,V. Chu,C. Müller, R. Streubel, Dalton Trans. 2010, 39, 3472-3481. [10] R. Streubel, J.M. Villalba Franco, G Schnakenburg, A. Espinosa Ferao, Chem. Commun., 2012, 48, 5986–5988.

  6. Reactivity of oxaphosphirane and azaphosphiridine complexes M = Cr, Mo, W • Ring expansion R’, R’’ = alkyl, aryl, H • Ring opening R= CH(SiMe3)2 • Deoxygenation R = C5Me5 R = CPh3 Example of a ring opening [11]M. Bode, G. Schnakenburg, P. G. Jones and R. Streubel, Organometallics, 2008, 11, 2664-2667. 6

  7. Objective

  8. Attempts to synthesize P-Cp* substituted azaphosphiridine complexes A + B

  9. A

  10. 31P = -34.5 ppm 1JW,P = 272 Hz 70 % yield W P C3 C2 N O C6

  11. r.t. >3 h r.t. 2 h r.t. 60 min r.t. 10 min +20 °C +10 °C 0 °C -5 °C -10 °C -20 °C -30 °C -40 °C -50 °C -60 °C -70 °C

  12. A. Espinosa B3LYP-D3/def2-TZVP 22.30 Erel (kcal/mol) 15.23 TS not yet located 1.14 -1.13 0.00 -3.15 -9.72 Reaction coordinate

  13. d31P = 225.9 ppm 1JW,P = 228.4 Hz Toluene, reflux 40 °C Toluene Up to65 % conversion W N P C5 F C2 227.0 ppm 230.8 Hz 40 % yield

  14. Up to 14 % conversion 227.0 ppm 230.8 Hz -27.0 ppm 275.8 Hz 5 h 30 min 0 min

  15. Proposed intermediate Erel (kcal/mol) A. Espinosa B3LYP-D3/def2-TZVP 9.13 0.54 0.00

  16. Twoproducts (structuralisomers) W P N C7 C8 40 % yield O

  17. Oneproduct [3+2] W P N1 O N2 C2 50 % Yield 144.8 ppm 1JW,P =285.7 Hz

  18. Summary

  19. Outlook • Studies on substituent effectson the azaphosphiridine ring opening • Synthesis of novel cage ligands usingthisprecursor system • Decomplexationof N,P,C-cageligands

  20. Acknowledgements • Prof. Dr. R. Streubel • Dr. A. Espinosa(Theory) • Dr. G. Schnakenburg (X-ray) • Analytics (NMR, MS, EA) • Research Group Streubel • University of Bonn • €€ DFG €€ • Cost cm0802 • „PhoSciNet“ • EWPC 10 Organizers

  21. Thank you for your kind attention

  22. Majoral et al, 1989 [2] [2] N. Dufour, A.-M. Caminade, J.-P. Majoral, Tetrahedron Lett. 1989, 30, 4813-4814.

  23. [15] J. Wit,G.van Eijkel, M. Schakel, K. Lammertsma, Tetrahedron, 2000, 56, 137.

  24. Cr BCP = Bond Critical Point P N C O

  25. Cowley et al. 1987 A. Cowley, R. Geerts, and C. NunnTetrahedron, J. Am. Chem. Soc. 1987, 109, 6523-6524.

  26. B. Sterenberg, K. Udachin, and A. CartyTetrahedron, Organometallics, 2001, 20, 4463-4465.

  27. *[17] S. Fankel,H. Helten,G. von Frantzius, G. Schnakenburg,J. Daniels,V. Chu,C. Müller, R. Streubel, Dalton Trans. 2010, 39, 3472-3481. *[18] José Manuel Villalba Franco, Diplomarbeit, Universität Bonn, 2010.

  28. r.t. 3 h r.t. 2 . r.t. 60 mins r.t. 10 min +20 °C +10 °C 0 °C -5 °C -10 °C -20 °C -30 °C -40 °C -50 °C -60 °C -70 °C

  29. Homodesmic Ring Opening Reaction of azaphosphiridines

  30. First phosphinidine complex A. Marinetti, F. Mathey, J. Fischer, A. Mitschler, JACS,1982, 104,4484.

  31. ? 226 to 227 ppm 1JW,P = 228 to 231 Hz 65% conv. ~ -26 to -35.0 ppm 1JW,P = 268 to 276 Hz

  32. 31P d = 225.9 ppm 1JW,P = 228.4 Hz Up to 65% r.t. 45 °C 60 °C 75 °C 75 °C 1h

  33. Posible intermediates for the isomerization

  34. -3.8 ppm 1JW,P =277.6 Hz 83% -0.3 ppm 1JW,P =280.7 Hz 17%

  35. W 144.8ppm 1JW,P =285.7 Hz P N1 O N2

  36. 1st TS 1st Int. P-N = 1.747 Å C-C = 1.412 Å C-C = 1.489 Å P-N = 1.815 Å P-N = 1.726 Å C-C = 1.368 Å C-N = 1.356 Å C-C = 1.481 Å 1st Int. Conform. C-C = 1.432 Å

  37. Phosphinidene Complex P-N = 1.647 Å P-C = 3.302 Å P-C = 3.383 Å 2nd cage 1st cage

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