The Aromaticity of Polyphosphaphospholes Decreases with the Pyramidality of the Tricoordinate Phosphorus

Inorganic Chemistry

Volumn 37, Issue 17, 1998, Pages 4413-4420

  Dransfeld, Alk ^a   Nyulászi, László ^a,b   Von Schleyer, Paul Ragué ^a  

^a UNIVERSITY OF ERLANGEN NUREMBERG   (Germany)

^b BUDAPEST UNIVERSITY OF TECHNOLOGY AND ECONOMICS   (Hungary)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0542373374     PISSN: 00201669     EISSN: None     Source Type: Journal    
DOI: 10.1021/ic971385y     Document Type: Article

References (58)

1. Baldridge, K. K.; Gordon, M. S. J. Am. Chem. Soc. 1988, 110, 4204.
2. Nyulászi. L.; Veszprémi, T.; Réffy, J.; Burkhardt, B.; Regitz, M. J. Am. Chem. Soc. 1992, 114, 9080.
3. Minkin, V. I.; Glukhovtsev, M. N.; Simkin, B. Ya. Aromaticity and Antiaromaticity - Electronic and Structural Aspects; J. Wiley: New York, 1994; p 48.
4. Schleyer, P. v. R.; Freeman, P. K.; Jiao, H.; Goldfuss, B. Angew. Chem., Int. Ed Engl. 1995, 34, 337.
5. Schleyer, P. v. R.; Maerker, C.; Dransfeld, A.; Jiao, H.; Hommes, N. v. E. J. Am. Chem. Soc. 1996, 118, 6317.
6. Pitzer, K. S. J. Am. Chem. Soc. 1948, 70, 2140.
7. Schmidt, M. W.; Gordon, M. S. Inorg. Chem. 1986, 25, 248.
8. Schmidt, M. W.; Truong, P. N.; Gordon, M. S. J. Am. Chem. Soc. 1987, 109, 5217.
9. Schleyer, P. v. R.; Kost, D. J. Am. Chem. Soc. 1988, 110, 2105.
10. Weston, R. E., Jr. J. Am. Chem. Soc. 1954, 76, 2645. Kapp, J.; Milan, R.; Schleyer, P. v. R. J. Am. Chem. Soc. 1996, 118, 5745. This phenomenon is often called an "inert s pair effect". For a detailed discussion of its origin, see: Kutzelnigg, W. Angew. Chem., Int. Ed. Engl. 1984, 23, 272.
11. Weston, R. E., Jr. J. Am. Chem. Soc. 1954, 76, 2645. Kapp, J.; Milan, R.; Schleyer, P. v. R. J. Am. Chem. Soc. 1996, 118, 5745. This phenomenon is often called an "inert s pair effect". For a detailed discussion of its origin, see: Kutzelnigg, W. Angew. Chem., Int. Ed. Engl. 1984, 23, 272.
12. Weston, R. E., Jr. J. Am. Chem. Soc. 1954, 76, 2645. Kapp, J.; Milan, R.; Schleyer, P. v. R. J. Am. Chem. Soc. 1996, 118, 5745. This phenomenon is often called an "inert s pair effect". For a detailed discussion of its origin, see: Kutzelnigg, W. Angew. Chem., Int. Ed. Engl. 1984, 23, 272.
13. (a) Andose, J. D.; Rauk, A.; Mislow, K. J. Am. Chem. Soc. 1974, 96, 6904,
14. (b) Reviews on phospholes: Mathey, F. Chem. Rev. 1988, 88, 437. Hughes, A. N. In Handbook of Organophosphorus Chemistry, Robert, E., Ed.; Marcel Dekker: New York, 1993. Quin, L. D. in Comprehensive Heterocyclic Chemistry; Katritzky, A. R., Ed.; Pergamon: Oxford, England, 1996; p 757.
15. (b) Reviews on phospholes: Mathey, F. Chem. Rev. 1988, 88, 437. Hughes, A. N. In Handbook of Organophosphorus Chemistry, Robert, E., Ed.; Marcel Dekker: New York, 1993. Quin, L. D. in Comprehensive Heterocyclic Chemistry; Katritzky, A. R., Ed.; Pergamon: Oxford, England, 1996; p 757.
16. (b) Reviews on phospholes: Mathey, F. Chem. Rev. 1988, 88, 437. Hughes, A. N. In Handbook of Organophosphorus Chemistry, Robert, E., Ed.; Marcel Dekker: New York, 1993. Quin, L. D. in Comprehensive Heterocyclic Chemistry; Katritzky, A. R., Ed.; Pergamon: Oxford, England, 1996; p 757.
17. Malar, P. E. J. J. Org. Chem. 1992, 57, 3694.
18. Mathey, F. Coord. Chem. Rev. 1994, 137, 1.
19. Kapp, J.; Schade, C.; El-Nahasa, A. M.; Schleyer, P. v. R. Angew. Chem., Int. Ed. Engl. 1996, 35, 2236.
20. Nyulászi, L. J. Phys. Chem. 1995, 99, 586.
21. Chesnut, D. B.; Quin, L. D. J. Am. Chem. Soc. 1994, 116, 9638.
22. Nyulászi, L. J. Phys. Chem. 1996, 100, 6194.
23. Baudler, M.; Akpapoglou, S.; Ouzounis, D.; Wasgestian, F.; Meinigke, B.; Budwkiewicz, H.; Münster, H. Angew. Chem., Int. Ed. Engl. 1988, 27, 288.
24. Glukhovtsev, M. N.; Dransfeld, A.; Schleyer, P. v. R. J. Phys. Chem. 1996, 100, 13447.
25. Nyulászi, L. Inorg. Chem. 1996, 35, 4690.
26. Schmidpeter, A.; Thiele, M. Angew. Chem., Int. Ed. Engl. 1991, 30, 308.
27. Jochem, G.; Nöth, H.; Schmidpeter, A. Chem. Ber. 1996, 129, 1083.
28. Nyulászi, L.; Nixon, J. F. J. Organomet. Chem., in press.
29. 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 (8), 1083.
30. Caliman, V.; Hitchcock, P. B.; Nixon, J. F. J. Chem. Soc., Chem. Commun. 1995, 1661.
31. Caliman, V.; Hitchcock, P. B.; Nixon, J. F.; Nyulássi, L.; Sakarya, N. J. Chem. Soc., Chem. Commun. 1997, 1301.
32. Keglevich, Gy.; Böcskei, Zs.; Keserü, Gy.; Ujszászi, K.; Quin, L. D.;J. Am. Chem. Soc. 1997, 119, 5095.
33. Nyulászi, L.; Keglevich, G.; Quin, L. D. J. Org. Chem. 1996, 61, 7808.
34. 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 94, revision E.2; Gaussian, Inc., Pittsburgh, PA. 1995.
35. Wolinski, K.; Hinton, J.; Pulay, P. J. Am. Chem. Soc. 1990, 112, 8251.
36. Cheeseman, J. R.; Trucks, G. W.; Keith, T. A.; Frisch, M. J. J. Chem. Phys. 1996, 104, 5497.
37. While diffuse functions have an appreciable effect (-0,4 to + 5.1 ppm, 6-31G* compared to 6-31+G*) on the NICS values, further basis set extensions result only in small changes (less than 0.3 ppm for benzene, phosphole) comparing 6-31-G* (see ref 5) with 6-311++G(2d,p) on MP2/6-31G* geometries.
38. The aromatic system in polyphosphaphospholes comprises the endocyclic carbon and phosphorus atoms.
39. Malkin, V. G.; Malkina, O. L.; Salahub, D. R. Chem. Phys. Lett. 1993, 204, 80.
40. Malkin, V. G.; Malkina, O. L.; Casida, M. E.; Salahub, D. R. J. Am. Chem. Soc. 1994, 116, 5898.
41. Kutzelnigg, W.; Fleischer, U.; Schindler, M. NMR 1990, 23, 190.
42. Pipek, J.; Mezey, P. G. J. Chem. Phys. 1989, 90, 4916.
43. Bird, C. W. Tetrahedron 1985, 41, 1409.
44. Nyulászi, L.; Vámai, P.; Veszprémi, T. J. Mol. Struct. (THEOCHEM) 1995, 358, 55.
45. Gordy, W. J. Chem. Phys. 1947, 15, 305.
46. 2) = 2.297, and R(HP-PH) = 2.051.
47. Schoeller, W. W. J. Mol. Struct. (THEOCHEM) 1993, 284, 61.
48. Jug, K. J. Org. Chem. 1983, 48, 1344.
49. Since the Gordy constants are derived from neutral reference compounds they are not appropriate for anions. Thus neither BI nor BDSHRT values were calculated for the anions (e.g., in Table 1),
50. Nyuläszi, L.; Veszprémi, T.; Réffy, J. J. Phys. Chem. 1993, 97, 4011.
51. Schleyer, P. v. R.; Jiao, H.; Hommes, N. J. v. E.; Malkin, V. G.; Malkina, O. J. J. Am. Chem. Soc. 1997, 118, 12669.
52. It is known that the in-plane complex formation of dicoordinate phosphorus with d elements results in slight shortening of either bond at the phosphorus atom. Appel, R. In Multiple Bonds and Low Coordination in Phosphorus Chemistry; Regitz, M., Scherer, O. J., Eds.; Georg Thieme Verlag: Stuttgart, 1990; p 157.
53. The MP2(fc)/6-31G* ASE energies of 1, 3b, and 5 are 8.7, 12.3, and 17.0 Kcal/mol, respectively.
54. Wiberg, K. B. Tetrahedron 1968, 24, 1083.
55. Schoeller, W. W.; Lerch, C. Inorg. Chem. 1986, 25, 576.
56. The description of the bonding about, tricoordinate phosphorus with two double and one single bond appears even in the most recent literature (e.g. Lamande, L.; Dillon, K.; Wolf, R. Phosphorus, Sulfur Silicon Relat. Elem. 1995, 103, 1). Nevertheless, this representation does not account properly for the delocalization of the phosphorus lone pair.
57. Reed, A. E.; Schleyer, P. v. R. J. Am. Chem. Soc. 1990, 112, 1434.
58. Magnusson, E. J. Am. Chem. Soc. 1993, 115, 1051.