Symmetrical and unsymmetrical diphosphanes with diversified alkyl, aryl and amino substituents - Publication - Bridge of Knowledge


Symmetrical and unsymmetrical diphosphanes with diversified alkyl, aryl and amino substituents


We present the comprehensive study of diphosphanes with diversified substituents regarding their syntheses, structures, and properties. To this end, we have synthesized a series of novel unsymmetrical alkyl, aryl and amino-substituted diphosphanes of the general formula R1R2P-PR3R4 (where R1, R2, R3, R4 = tBu, Ph, Et2N or iPr2N) via salt metathesis reactionof halophosphanes with metal phosphides in high yield. We vastly expanded this group of compounds by obtaining the first mono- and tri-amino-substituted systems. The structures of isolated compounds were characterized by NMR spectroscopy and X-ray diffraction. The isolated unsymmetrical diphosphanes have no tendency to rearrange to corresponding symmetrical species. Additionally, we proposed the general classification of diphosphanes based on the number of different groups attached to phosphorus atoms and their distribution within a molecule. To investigate the impact of substituents on the properties of P-centers and a molecule as a whole we conducted a DFT study on electronic and steric properties of obtained systems. The experimental and theoretical results can be very useful for designing P-P systems with desired properties.


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DALTON TRANSACTIONS pages 16885 - 16894,
ISSN: 1477-9226
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Bibliographic description:
Szynkiewicz N., Ponikiewski Ł., Grubba R.: Symmetrical and unsymmetrical diphosphanes with diversified alkyl, aryl and amino substituents// DALTON TRANSACTIONS. -, iss. 47 (2018), s.16885-16894
Digital Object Identifier (open in new tab) 10.1039/c8dt03775b
Bibliography: test
  1. L. Maier, in Progress in Inorganic Chemistry, 1963, pp. 27- 210. open in new tab
  2. A. H. Cowley, Chem. R, 1970, 227, 419-419.
  3. H. Goldwhite, J. Kaminski, G. Millhauser, J. Ortiz, M. Vargas, L. Vertal, M. F. Lappert and S. J. Smith, J. Organomet. Chem., 1986, 310, 21-25. open in new tab
  4. R. Grubba, M. Zauliczny, Ł. Ponikiewski and J. Pikies, Dalt. Trans., 2016, 45, 4961-4964. open in new tab
  5. E. Niecke, H. R. G. Bender, M. Nieger and H. Westermann, Zeitschrift für Anorg. und Allg. Chemie, 1994, 620, 1194- 1202.
  6. G. Fritz and P. Scheer, Chem. Rev., 2000, 100, 3341-3401. open in new tab
  7. W. Domańska-Babul, K. Baranowska, R. Grubba, E. Matern and J. Pikies, Polyhedron, 2007, 26, 5491-5496. open in new tab
  8. S. Blair, K. Izod, R. Taylor and W. Clegg, J. Organomet. Chem., 2002, 656, 43-48. open in new tab
  9. R. Grubba, Ł. Ponikiewski, J. Chojnacki and J. Pikies, Acta Crystallogr. Sect. E Struct. Reports Online, 2009, 65, o2214- o2214. open in new tab
  10. D. Förster, M. Nieger and D. Gudat, Organometallics, 2011, 30, 2628-2631. open in new tab
  11. O. Puntigam, D. Förster, N. A. Giffin, S. Burck, J. Bender, F. Ehret, A. D. Hendsbee, M. Nieger, J. D. Masuda and D. Gudat, Eur. J. Inorg. Chem., 2013, 2013, 2041-2050. open in new tab
  12. N. A. Giffin, A. D. Hendsbee, T. L. Roemmele, M. D. open in new tab
  13. Lumsden, C. C. Pye and J. D. Masuda, Inorg. Chem., 2012, 51, 11837-11850.
  14. S. Burck, D. Gudat and M. Nieger, Angew. Chemie -Int. Ed., 2004, 43, 4801-4804. open in new tab
  15. S. Burck, K. Götz, M. Kaupp, M. Nieger, J. Weber, J. S. Auf Der Günne and D. Gudat, J. Am. Chem. Soc., 2009, 131, 10763-10774. open in new tab
  16. S. Burck, D. Gudat and M. Nieger, Organometallics, 2009, 28, 1447-1452. open in new tab
  17. O. Puntigam, I. Hajdók, M. Nieger, M. Niemeyer, S. Strobel and D. Gudat, Zeitschrift für Anorg. und Allg. Chemie, 2011, 637, 988-994. open in new tab
  18. S. Burck, I. Hajdók, M. Nieger, D. Bubrin, S. Schulze and D. open in new tab
  19. Gudat, Zeitschrift fur Naturforsch. -Sect. B J. Chem. Sci., 2009, 64, 63-72.
  20. D. L. Dodds, M. F. Haddow, A. G. Orpen, P. G. Pringle and G. Woodward, Organometallics, 2006, 25, 5937-5945. open in new tab
  21. D. L. Dodds, J. Floure, M. Garland, M. F. Haddow, T. R. Leonard, C. L. McMullin, A. G. Orpen and P. G. Pringle, Dalt. Trans., 2011, 40, 7137-7146. open in new tab
  22. A. A. M. Ali and R. K. Harris, J. Chem. Soc. Dalt. Trans., 1983, 88, 583. open in new tab
  23. C. Goh, B. M. Segal, J. Huang, J. R. Long and R. H. Holm, J. Am. Chem. Soc., 1996, 118, 11844-11853. open in new tab
  24. S. Loss, C. Widauer and H. Grützmacher, Angew. Chemie - Int. Ed., 1999, 38, 3329-3331. open in new tab
  25. J. Mahnke, A. Zanin, W.-W. du Mont, F. Ruthe and P. G. Jones, Zeitschrift für Anorg. und Allg. Chemie, 1998, 624, 1447-1454. open in new tab
  26. G. Becker, O. Mundt and M. Rössler, Zeitschrift fur Anorg. und Allg. Chemie, 1980, 468, 55-67. open in new tab
  27. D. C. Pestana and P. P. Power, J. Am. Chem. Soc., 1991, 30, 528-535. open in new tab
  28. V. Gandon, J. B. Bourg, F. S. Tham, W. W. Schoeller and G. Bertrand, Angew. Chemie -Int. Ed., 2008, 47, 155-159. open in new tab
  29. H. Nöth, B. Gemünd and R. T. Paine, Eur. J. Inorg. Chem., 2007, 2007, 4282-4297. open in new tab
  30. J. Pikies, E. Baum, E. Matern, J. Chojnacki, R. Grubba and A. Robaszkiewicz, Chem. Commun., 2004, 98, 2478-2479. open in new tab
  31. R. Grubba, K. Baranowska, D. Gudat and J. Pikies, Organometallics, 2011, 30, 6655-6660. open in new tab
  32. T. Kruczyński, R. Grubba, K. Baranowska and J. Pikies, Polyhedron, 2012, 39, 25-30. open in new tab
  33. A. Wiśniewska, A. Łapczuk-Krygier, K. Baranowska, J. Chojnacki, E. Matern, J. Pikies and R. Grubba, Polyhedron, 2013, 55, 45-48. open in new tab
  34. W. Domańska-Babul, J. Chojnacki, E. Matern and J. Pikies, Dalt. Trans., 2009, 668504, 146-151. open in new tab
  35. R. Grubba, A. Wiśniewska, K. Baranowska, E. Matern and J. Pikies, Dalt. Trans., 2011, 40, 2017. open in new tab
  36. R. Grubba, K. Baranowska, J. Chojnacki and J. Pikies, Eur. J. Inorg. Chem., 2012, 1, 3263-3265. open in new tab
  37. R. Grubba, A. Wiśniewska, Ł. Ponikiewski, M. Caporali, M. Peruzzini and J. Pikies, Eur. J. Inorg. Chem., 2014, 1811- 1817. open in new tab
  38. R. Grubba, A. Ordyszewska, K. Kaniewska, Ł. Ponikiewski, J. Chojnacki, D. Gudat and J. Pikies, Inorg. Chem., 2015, 54, 8380-8387. open in new tab
  39. R. Grubba, A. Ordyszewska, Ł. Ponikiewski, D. Gudat and J. Pikies, Dalt. Trans., 2016, 45, 2172-2179. open in new tab
  40. M. Zauliczny, R. Grubba, Ł. Ponikiewski and J. Pikies, Polyhedron, 2017, 123, 353-360. open in new tab
  41. Ł. Ponikiewski, A. Ziółkowska and J. Pikies, Inorg. Chem., 2017, 56, 1094-1103. open in new tab
  42. S. Burck, D. Förster and D. Gudat, Chem. Commun. (Camb)., 2006, 2810-2812. open in new tab
  43. M. Blum, O. Puntigam, S. Plebst, F. Ehret, J. Bender, M. Nieger and D. Gudat, Dalt. Trans., 2016, 45, 1987-1997. open in new tab
  44. H. Niebergall and B. Langenfeld, Chem. Ber., 1962, 95, 64- 76. open in new tab
  45. K. B. Borisenko and D. W. H. Rankin, J. Chem. Soc. Dalt. Trans., 2002, 3135. open in new tab
  46. K. B. Borisenko and D. W. H. Rankin, Inorg. Chem., 2003, 42, 7129-7136. open in new tab
  47. J.-D. Guo, S. Nagase and P. P. Power, Organometallics, 2015, 34, 2028-2033. open in new tab
  48. P. P. Power, Chem. Rev., 2003, 103, 789-809. open in new tab
  49. S. L. Hinchley, C. A. Morrison, D. W. H. Rankin, C. L. B. Macdonald, R. J. Wiacek, A. Voigt, A. H. Cowley, M. F. Lappert, G. Gundersen, J. A. C. Clyburne and P. P. Power, J. Am. Chem. Soc., 2001, 123, 9045-9053. open in new tab
  50. H. C. E. McFarlane and W. McFaralane, J. Chem. Soc. Chem. Commun., 1972, 1189. open in new tab
  51. S. Aime, R. K. Harris, E. M. McVicker and M. Fild, J. Chem. Soc., Dalt. Trans., 1976, 2144-2153. open in new tab
  52. R. K. Harris, E. M. Norval (née McVicker) and M. Fild, J. Chem. Soc., Dalt. Trans., 1979, 826-831. open in new tab
  53. A. A. M. Ali and R. K. Harris, Dalt. Trans., 1988, 2775-2780. open in new tab
  54. C. Dörken, Berichte der Dtsch. Chem. Gesellschaft, 1888, 21, 1505-1515. open in new tab
  55. W. Kuchen and H. Buchwald, Chem. Ber., 1959, 92, 227- 231. open in new tab
  56. V. P. W. Böhm and M. Brookhart, Angew. Chemie Int. Ed., 2001, 40, 4694-4696. open in new tab
  57. A. B. Burg, J. Am. Chem. Soc., 1961, 83, 2226-2231. open in new tab
  58. M. J. S. Gynane, A. Hudson, M. F. Lappert and P. P. Power, J. Chem. Soc., Chem. Commun., 1976, 623-624. open in new tab
  59. K. Issleib and K. Krech, Chem. Ber., 1965, 98, 1093-1096. open in new tab
  60. W. A. Henderson, M. Epstein and F. S. Seichter, J. Am. Chem. Soc., 1963, 85, 2462-2466. open in new tab
  61. H. Nöth and H.-J. Vetter, Chem. Ber., 1961, 94, 1505-1516. open in new tab
  62. H. Nöth and H.-J. Vetter, Chem. Ber., 1963, 96, 1479-1484. open in new tab
  63. K. Issleib and W. Seidel, Chem. Ber., 1959, 92, 2681-2694. open in new tab
  64. M. Baudler and K. Glinka, Chem. Rev., 1993, 93, 1623- 1667. open in new tab
  65. L. R. Avens, L. V. Cribbs and J. L. Mills, Inorg. Chem., 1989, 28, 211-214. open in new tab
  66. R. Waterman, Curr. Org. Chem., 2008, 12, 1322-1339. open in new tab
  67. R. Waterman, Curr. Org. Chem., 2012, 16, 1313-1331. open in new tab
  68. K. Kaniewska, A. Dragulescu-Andrasi, Ł. Ponikiewski, J. Pikies, S. A. Stoian and R. Grubba, Eur. J. Inorg. Chem., 2018, 2018, 4298-4308. open in new tab
  69. H. Schneider, D. Schmidt and U. Radius, Chem. Commun., 2015, 51, 10138-10141. open in new tab
  70. K. Schwedtmann, R. Schoemaker, F. Hennersdorf, A. Bauzá, A. Frontera, R. Weiss and J. J. Weigand, Dalt. Trans., 2016, 45, 11384-11396. open in new tab
  71. K. Issleib and M. Hoffmann, Chem. Ber., 1966, 99, 1320- 1324. open in new tab
  72. S. L. Hinchley, H. E. Robertson, K. B. Borisenko, A. R. open in new tab
  73. Turner, B. F. Johnston, D. W. H. Rankin, M. Ahmadian, J. N. Jones and A. H. Cowley, Dalt. Trans., 2004, 2469-2476. open in new tab
  74. J. Heinicke and R. Kadyrov, J.Organometal.Chem, 1996, 520, 2-8. open in new tab
  75. J. E. Nycz, Phosphorus, Sulfur Silicon Relat. Elem., 2009, 184, 2605-2612. open in new tab
  76. F. Knoch, R. Appel and B. Brück, Zeitschrift für Krist., 1995, 210, 314-314. open in new tab
  77. P. P. Graczyk and M. Mikolajczyk, J. Org. Chem., 1996, 61, 2995-3002. open in new tab
  78. D. J. Liptrot and P. P. Power, Nat. Rev. Chem., 2017, 1, 0004. open in new tab
  79. A. Zschunke, M. Riemer, F. Krech and K. Issleib, Phosphorus Sulfur Relat. Elem., 1985, 22, 349-352. open in new tab
  80. J. Meiners, A. Friedrich, E. Herdtweck and S. Schneider, Organometallics, 2009, 28, 6331-6338. open in new tab
  81. R. B. King and N. D. Sadanani, Synth. React. Inorg. Met. Chem., 1985, 15, 149-153. open in new tab
  82. W. Zeiß, C. Feldt, J. Weis and G. Dunkel, Chem. Ber., 1978, 111, 1180-1194. open in new tab
  83. S. Schweizer, J. M. Becht and C. Le Drian, Tetrahedron, 2010, 66, 765-772. open in new tab
  84. A. H. Cowley, M. J. S. Dewar, W. R. Jackson and W. B. Jennings, J. Am. Chem. Soc., 1970, 92, 5206-5213. open in new tab
  85. J. Böske, E. Niecke, E. Ocando-Mavarez, J. P. Majoral and G. Bertrand, Inorg. Chem., 1986, 25, 2695-2698.
  86. G. M. Sheldrick, Acta Crystallogr. Sect. A Found. Crystallogr., 2008, 64, 112-122. open in new tab
  87. L. J. Farrugia, J. Appl. Crystallogr., 2012, 45, 849-854. open in new tab
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