Aromatic compounds with planar tricoordinate phosphorus

Tetrahedron

Volumn 56, Issue 1, 2000, Pages 79-84

  Nyulászi, László ^a  

^a BUDAPEST UNIVERSITY OF TECHNOLOGY AND ECONOMICS   (Hungary)

Author keywords

Aromaticity; Cyclic compounds; Tricoordinate phosphorus

Indexed keywords

AROMATIC COMPOUND; PHOSPHORUS;

CHEMICAL BINDING; CHEMICAL REACTION; CHEMICAL STRUCTURE; CONFERENCE PAPER; PRIORITY JOURNAL; REACTION ANALYSIS; STRUCTURE ANALYSIS; SYNTHESIS;

EID: 0038570516     PISSN: 00404020     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4020(99)00775-9     Document Type: Conference Paper

References (67)

1. Regitz, M.; Scherer, O. Multiple Bonds and Low Coordination in Phosphorus Chemistry; Georg Thieme: Stuttgart, 1990, p 1.
2. (a) Nyulászi, L.; Veszprémi, T.; Réffy, J. J. Phys. Chem. 1993, 97, 4011.
3. (b) The similar chemical reactivity of the two bonds has been described in: Mathey, F. Acc. Chem. Res. 1992, 25, 90; Appel, R. Pure Appl. Chem. 1987, 59, 977; Dillon, K. B.; Mathey, F.; Nixon, J. F. In Phosphorus, the Carbon Copy; Wiley: Chichester, 1998.
4. (b) The similar chemical reactivity of the two bonds has been described in: Mathey, F. Acc. Chem. Res. 1992, 25, 90; Appel, R. Pure Appl. Chem. 1987, 59, 977; Dillon, K. B.; Mathey, F.; Nixon, J. F. In Phosphorus, the Carbon Copy; Wiley: Chichester, 1998.
5. (b) The similar chemical reactivity of the two bonds has been described in: Mathey, F. Acc. Chem. Res. 1992, 25, 90; Appel, R. Pure Appl. Chem. 1987, 59, 977; Dillon, K. B.; Mathey, F.; Nixon, J. F. In Phosphorus, the Carbon Copy; Wiley: Chichester, 1998.
6. Apart from Ref 2a see: (a) Baldridge, K. K. J. Am. Chem. Soc. 1988, 110, 4204. (b) Jonas, V.; Frenking, G. Chem. Phys. Lett. 1993, 210, 211.
7. Apart from Ref 2a see: (a) Baldridge, K. K. J. Am. Chem. Soc. 1988, 110, 4204. (b) Jonas, V.; Frenking, G. Chem. Phys. Lett. 1993, 210, 211.
8. 3-phosphorus and a transition metal.
9. Schwerdtferger, P.; Laakkonen, L.; Pyykkö, P. J. Chem. Phys. 1992, 96, 6807.
10. For comparable aromaticity measures see: (a) Ref. 3a; Nyulászi, L.; Veszprémi, T.; Réffy, J.; Burkhardt, B.; Regitz, M. J. Am. Chem. Soc. 1992, 114, 9080. (b) Minkin, V. I.; Glukhotsev, M. N.; Simkin, B. Ya.; In Aromaticity and Antiaromaticity - Electronic and Structural Aspects; Wiley: New York, 1994. (c) Schleyer, P. v. R.; Freeman, P. K.; Jiao H.; Goldfuss, B. Angew. Chem., Int. Ed. Engl. 1995, 34, 337.
11. For comparable aromaticity measures see: (a) Ref. 3a; Nyulászi, L.; Veszprémi, T.; Réffy, J.; Burkhardt, B.; Regitz, M. J. Am. Chem. Soc. 1992, 114, 9080. (b) Minkin, V. I.; Glukhotsev, M. N.; Simkin, B. Ya.; In Aromaticity and Antiaromaticity -Electronic and Structural Aspects; Wiley: New York, 1994. (c) Schleyer, P. v. R.; Freeman, P. K.; Jiao H.; Goldfuss, B. Angew. Chem., Int. Ed. Engl. 1995, 34, 337.
12. For comparable aromaticity measures see: (a) Ref. 3a; Nyulászi, L.; Veszprémi, T.; Réffy, J.; Burkhardt, B.; Regitz, M. J. Am. Chem. Soc. 1992, 114, 9080. (b) Minkin, V. I.; Glukhotsev, M. N.; Simkin, B. Ya.; In Aromaticity and Antiaromaticity - Electronic and Structural Aspects; Wiley: New York, 1994. (c) Schleyer, P. v. R.; Freeman, P. K.; Jiao H.; Goldfuss, B. Angew. Chem., Int. Ed. Engl. 1995, 34, 337.
13. (d) Schleyer, P. v. R.; Maerker, C.; Dransfeld, A.; Jiao, H.; Hommes, N. v. E. J. Am. Chem. Soc. 1996, 118, 6317.
14. Nyulászi, L.; Belghazi, A.; Kis-Szétsi, S.; Veszprémi, T.; Heinicke, J. J. Mol. Struct. (Theochem) 1994, 313, 73.
15. Kapp, J.; Schade, C.; El-Nahasa, A. M.; Schleyer, P. v. R. Angew. Chem., Int. Ed. Engl. 1996, 35, 2236.
16. Egan, W.; Tang, R.; Zon, G.; Mislow, K. J. Am. Chem. Soc. 1970, 92, 1443. Mislow has interpreted the difference between the phosphole and phospholane inversion barriers, measured by dynamic NMR spectroscopy, as a result of the aromatic stabilization of the planar structure of the former species. Early CNDO/S calculations (Andose, J. D.; Rauk, A.; Mislow, K. J. Am. Chem. Soc. 1974, 96, 6904) were in agreement with this finding.
17. Egan, W.; Tang, R.; Zon, G.; Mislow, K. J. Am. Chem. Soc. 1970, 92, 1443. Mislow has interpreted the difference between the phosphole and phospholane inversion barriers, measured by dynamic NMR spectroscopy, as a result of the aromatic stabilization of the planar structure of the former species. Early CNDO/S calculations (Andose, J. D.; Rauk, A.; Mislow, K. J. Am. Chem. Soc. 1974, 96, 6904) were in agreement with this finding.
18. Ab initio calculations gave full support to the aromaticity of the planar phosphole. (a) Chesnut D. B.; Quin, L. D. J. Am. Chem. Soc. 1994, 116, 5779. (b) Nyulászi, L. J. Phys. Chem. 1995, 99, 586.
19. Ab initio calculations gave full support to the aromaticity of the planar phosphole. (a) Chesnut D. B.; Quin, L. D. J. Am. Chem. Soc. 1994, 116, 5779. (b) Nyulászi, L. J. Phys. Chem. 1995, 99, 586.
20. Levin, C. C. J. Am. Chem. Soc. 1975, 97, 5649.
21. Glukhotsev, M. N.; Dransfeld, A.; Schleyer, P. v. R. J. Phys. Chem. 1996, 100, 13 447.
22. 3) has been synthesized (Igau, A.; Grützmacher, H.; Baceiredo, A.; Bertrand, G. J. Am. Chem. Soc. 1988, 110, 8782). This compound has a pronounced >P≡C-character due to the effect of the substituents.
23. 3) has been synthesized (Igau, A.; Grützmacher, H.; Baceiredo, A.; Bertrand, G. J. Am. Chem. Soc. 1988, 110, 8782). This compound has a pronounced >P≡C-character due to the effect of the substituents.
24. 3) has been synthesized (Igau, A.; Grützmacher, H.; Baceiredo, A.; Bertrand, G. J. Am. Chem. Soc. 1988, 110, 8782). This compound has a pronounced >P≡C-character due to the effect of the substituents.
25. 3) has been synthesized (Igau, A.; Grützmacher, H.; Baceiredo, A.; Bertrand, G. J. Am. Chem. Soc. 1988, 110, 8782). This compound has a pronounced >P≡C-character due to the effect of the substituents.
26. For a recent review on phosphinoboranes see Paine, R. T.; Nöth, H. Chem. Rev. 1995, 95, 343.
27. (a) Schade, C.; Schleyer, P. v. R. J. Chem. Soc., Chem. Commun. 1987, 1399.
28. (b) Coolidge, M. B.; Borden, W. T. J. Am. Chem. Soc. 1990, 112, 1704.
29. (c) Allen, T. N.; Scheiner, A. C.; Schäfer III, H. F. Inorg. Chem. 1990, 29, 1930.
30. Bartlett, R. A.; Rasika Dias, H. V.; Power, P. P. Inorg. Chem. 1988, 27, 3919.
31. Schoeller, W. W.; Lerch, C. Inorg. Chem. 1986, 25, 576; See also Schoeller, W. W. Bonding Properties of Low Coordinated Phosphorus Compounds. In Multiple Bonds and Low Coordination in Phosphorus Chemistry; Regitz, M., Scherer, O., Eds.; Georg Thieme: Stuttgart, 1990.
32. Schoeller, W. W.; Lerch, C. Inorg. Chem. 1986, 25, 576; See also Schoeller, W. W. Bonding Properties of Low Coordinated Phosphorus Compounds. In Multiple Bonds and Low Coordination in Phosphorus Chemistry; Regitz, M., Scherer, O., Eds.; Georg Thieme: Stuttgart, 1990.
33. Dransfeld, A.; Nyulászi, L.; Schleyer, P. v. R. Inorg. Chem. 1998, 37, 4413.
34. Dias, H. V. R.; Power, P. P. Angew. Chem. 1987, 99, 1320; J. Am. Chem. Soc. 1989, 111, 144.
35. Dias, H. V. R.; Power, P. P. Angew. Chem. 1987, 99, 1320; J. Am. Chem. Soc. 1989, 111, 144.
36. (a) Fink, W. H.; Richards, J. C. J. Am. Chem. Soc. 1991, 113, 3393.
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39. Nyulászi, L.; Szieberth, D.; Veszprémi, T. J. Org. Chem. 1995, 60, 1647.
40. Throughout the text the following aromaticity criteria are used: NICS - nucleous independent chemical shift, calculated at the ring center, as defined in Ref. 6d. Bird aromaticity index, developed from a statistical evaluation of the variation of the peripherical bond orders in the ring (Bird, C. W. Tetrahedron 1985, 41, 1409). Bond Shortening index, which is a consequence of the general increase of the bond orders, as a result of the aromatic stabilization ( Nyulászi, L.; Várnai, P.; Veszprémi, T. J. Mol. Struct. (Theochem) 1995, 358, 55 - see also for the definition of the semihomodesmotic (SHE) reaction for five membered rings).
41. Throughout the text the following aromaticity criteria are used: NICS - nucleous independent chemical shift, calculated at the ring center, as defined in Ref. 6d. Bird aromaticity index, developed from a statistical evaluation of the variation of the peripherical bond orders in the ring (Bird, C. W. Tetrahedron 1985, 41, 1409). Bond Shortening index, which is a consequence of the general increase of the bond orders, as a result of the aromatic stabilization ( Nyulászi, L.; Várnai, P.; Veszprémi, T. J. Mol. Struct. (Theochem) 1995, 358, 55 - see also for the definition of the semihomodesmotic (SHE) reaction for five membered rings).
42. The calculations were carried out by the Gaussian 94 package. While some data were published before, the present results are all recalculated at the B3LYP/6-311+G** level for the sake of uniformity. Gaussian 94, Revision E.2; Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Gill, P. M. W.; Johnson, B. G.; Robb, M. A.; Cheeseman, J. R.; Keith, T.; Petersson, G. A.; Montgomery, J. A.; Raghavachari, K.; Al-Laham, M. A.; Zakrzewski, V. G.; Ortiz, J. V.; Foresman, J. B.; Cioslowski, J.; Stefanov, B. B.; Nanayakkara, A.; Challacombe, M.; Peng, C. Y.; Ayala, P. Y.; Chen, W.; Wong, M. W.; Andres, J. L.; Replogle, E. S.; Gomperts, R.; Martin, R. L.; Fox, D. J.; Binkley, J. S.; Defrees, D. J.; Baker, J.; Stewart, J. P.; Head-Gordon, M.; Gonzalez, C.; Pople, J. A. Gaussian, Inc., Pittsburgh PA, 1995.
43. (a) Schmidpeter, A.; Thiele, M. Angew. Chem., Int. Ed. Engl. 1991, 30, 308.
44. (b) Gudat, D. XII Int. Conf. on Phosphorus Chem., Toulouse, 1992.
45. (c) Jochem, G.; Nöth, H.; Schmidpeter, A. Chem. Ber. 1996, 129, 1083.
46. (a) Quin, L. D.; Ionkin, A. S.; Kalgutkar, R.; Keglevich, Gy. Phosphorus, Sulfur 1996, 109-110, 433.
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48. (c) Nyulászi, L.; Keglevich, G.; Quin, L. D. J. Org. Chem. 1996, 61, 7808.
49. (d) Keglevich, Gy.; Böcskei, Zs.; Keserü, Gy.; Ujszászi, K.; Quin, L. D. J. Am., Chem. Soc. 1997, 119, 5095.
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51. Nyulászi, L.; Soós, L.; Keglevich, Gy. J. Organomet. Chem. 1998, 566, 29.
52. (a) Nyulászi, L. J. Phys. Chem. 1996, 100, 6194.
53. (b) Nyulászi, L. Inorg. Chem. 1996, 35, 4690.
54. 5H as a planar species has first been mentioned in Ref. 6b.
55. A failed attempt to synthesize pentaphosphole from pentaphospholide anion with alkyl-halide was reported (Baudler, M.; Akpapoglou, S.; Ouzounis, D.; Wasgestian, F.; Meinigke, B.; Budzikiewicz, H.; Münster, H. Angew. Chem., Int. Ed. Engl. 1988, 27, 288.
56. Caliman, V.; Hitchcock, P. B.; Nixon, J. F. J. Chem. Soc., Chem. Commun. 1995, 1661.
57. Cloke, F. G. N.; Hitchcock, P. B.; Hunnable, P.; Nixon, J. F.; Nyulászi, L.; Niecke, E.; Thelen, V. Angew. Chem., Int. Ed. Engl. 1998, 37, 1083.
58. Caliman, V.; Hitchcock, P. B.; Nixon, J. F.; Nyulászi, L.; Sakarya, N. J. Chem. Soc., Chem. Commun. 1997, 1301.
59. Mathey, F. Coord. Chem. Rev. 1994, 137, 1.
60. The NICS values calculated at the geometrical mean of the ring heavy atoms, might here also be influenced by the in plane σ bond.
61. Nyulászi, L.; Bergsträßer, U.; Regitz, M.; Schleyer, P. v. R. New. J. Chem. 1998, 651.
62. Niecke, E.; Fuchs, A.; Baumeister, F.; Nieger, M.; Schoeller, W. W. Angew. Chem., Int. Ed. Engl. 1995, 34, 555-557.
63. The difference of the calculated (Ref. 36) structure (with H-s at phosphorus) from the reported (Ref. 36) crystal structure is in agreement with the above surmise.
64. Kárpáti, T.; Nyulászi, L., to be published. The present results are at the B3LYP/3-21G(*) level.
65. Nyulászi, L.; Nixon, J. F. J. Organomet. Chem. 1999, 588, 28-31.
66. Nyulászi, L.; Regitz, M., to be published.
67. Bachrach, S. M.; Caliman, V.; Nixon, J. F. J. Chem. Soc., Chem. Commun. 1995, 2395.