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Volumn 566, Issue 1-2, 1998, Pages 29-35

Study of the planarization of the tricordinate phosphorus in phospholes; Photoelectron spectra and structure of partially planarized phospholes

Author keywords

Ab initio calculations; Aromaticity; Phospholes; Photoelectron spectra

Indexed keywords


EID: 0002849394     PISSN: 0022328X     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0022-328X(98)00685-8     Document Type: Article
Times cited : (39)

References (36)
  • 1
    • 0002712810 scopus 로고
    • For comprehensive works see:
    • For comprehensive works see: F. Mathey, Chem. Rev. 88 (1988) 437; A.N. Hughes, in: R. Engel (Ed.), Handbook of Organophosphorus Chemistry, Marcel Dekker, New York, 1992, Chapter 10; L.D. Quin, in: A. Katritzky, C. Rees, W.E.F.V. Scriven (Eds.), Comprehensive Heterocyclic Chemistry, Vol. 2, Pergamon, Oxford, England, 1996, Vol. 2, pp. 757-856. Aromaticity indices of different type are much smaller for phosphole than for other five membered rings; K.K. Baldridge, M.S. Gordon, J. Am. Chem. Soc. 110 (1988) 4204; L. Nyulászi, T. Veszprémi, J. Réffy, B. Burkhardt, M. Regitz, J. Am. Chem. Soc. 114 (1992) 9080; V.I. Minkin, M.N. Glukhotsev, B.Ya. Simkin, Aromaticity and Antiaromaticity - Electronic and Structural Aspects, Wiley, New York, 1994; P.v.R. Schleyer, P.K. Freeman, H. Jiao, B. Goldfuss, Angew. Chem. Int. Ed. Engl. 34 (1995) 337.
    • (1988) Chem. Rev. , vol.88 , pp. 437
    • Mathey, F.1
  • 2
    • 0040674467 scopus 로고
    • in: R. Engel (Ed.), Marcel Dekker, New York, Chapter 10;
    • For comprehensive works see: F. Mathey, Chem. Rev. 88 (1988) 437; A.N. Hughes, in: R. Engel (Ed.), Handbook of Organophosphorus Chemistry, Marcel Dekker, New York, 1992, Chapter 10; L.D. Quin, in: A. Katritzky, C. Rees, W.E.F.V. Scriven (Eds.), Comprehensive Heterocyclic Chemistry, Vol. 2, Pergamon, Oxford, England, 1996, Vol. 2, pp. 757-856. Aromaticity indices of different type are much smaller for phosphole than for other five membered rings; K.K. Baldridge, M.S. Gordon, J. Am. Chem. Soc. 110 (1988) 4204; L. Nyulászi, T. Veszprémi, J. Réffy, B. Burkhardt, M. Regitz, J. Am. Chem. Soc. 114 (1992) 9080; V.I. Minkin, M.N. Glukhotsev, B.Ya. Simkin, Aromaticity and Antiaromaticity - Electronic and Structural Aspects, Wiley, New York, 1994; P.v.R. Schleyer, P.K. Freeman, H. Jiao, B. Goldfuss, Angew. Chem. Int. Ed. Engl. 34 (1995) 337.
    • (1992) Handbook of Organophosphorus Chemistry
    • Hughes, A.N.1
  • 3
    • 84944050362 scopus 로고    scopus 로고
    • in: A. Katritzky, C. Rees, W.E.F.V. Scriven (Eds.), Vol. 2, Pergamon, Oxford, England, Aromaticity indices of different type are much smaller for phosphole than for other five membered rings;
    • For comprehensive works see: F. Mathey, Chem. Rev. 88 (1988) 437; A.N. Hughes, in: R. Engel (Ed.), Handbook of Organophosphorus Chemistry, Marcel Dekker, New York, 1992, Chapter 10; L.D. Quin, in: A. Katritzky, C. Rees, W.E.F.V. Scriven (Eds.), Comprehensive Heterocyclic Chemistry, Vol. 2, Pergamon, Oxford, England, 1996, Vol. 2, pp. 757-856. Aromaticity indices of different type are much smaller for phosphole than for other five membered rings; K.K. Baldridge, M.S. Gordon, J. Am. Chem. Soc. 110 (1988) 4204; L. Nyulászi, T. Veszprémi, J. Réffy, B. Burkhardt, M. Regitz, J. Am. Chem. Soc. 114 (1992) 9080; V.I. Minkin, M.N. Glukhotsev, B.Ya. Simkin, Aromaticity and Antiaromaticity - Electronic and Structural Aspects, Wiley, New York, 1994; P.v.R. Schleyer, P.K. Freeman, H. Jiao, B. Goldfuss, Angew. Chem. Int. Ed. Engl. 34 (1995) 337.
    • (1996) Comprehensive Heterocyclic Chemistry , vol.2 , pp. 757-856
    • Quin, L.D.1
  • 4
    • 33845280768 scopus 로고
    • For comprehensive works see: F. Mathey, Chem. Rev. 88 (1988) 437; A.N. Hughes, in: R. Engel (Ed.), Handbook of Organophosphorus Chemistry, Marcel Dekker, New York, 1992, Chapter 10; L.D. Quin, in: A. Katritzky, C. Rees, W.E.F.V. Scriven (Eds.), Comprehensive Heterocyclic Chemistry, Vol. 2, Pergamon, Oxford, England, 1996, Vol. 2, pp. 757-856. Aromaticity indices of different type are much smaller for phosphole than for other five membered rings; K.K. Baldridge, M.S. Gordon, J. Am. Chem. Soc. 110 (1988) 4204; L. Nyulászi, T. Veszprémi, J. Réffy, B. Burkhardt, M. Regitz, J. Am. Chem. Soc. 114 (1992) 9080; V.I. Minkin, M.N. Glukhotsev, B.Ya. Simkin, Aromaticity and Antiaromaticity - Electronic and Structural Aspects, Wiley, New York, 1994; P.v.R. Schleyer, P.K. Freeman, H. Jiao, B. Goldfuss, Angew. Chem. Int. Ed. Engl. 34 (1995) 337.
    • (1988) J. Am. Chem. Soc. , vol.110 , pp. 4204
    • Baldridge, K.K.1    Gordon, M.S.2
  • 5
    • 0040080846 scopus 로고
    • For comprehensive works see: F. Mathey, Chem. Rev. 88 (1988) 437; A.N. Hughes, in: R. Engel (Ed.), Handbook of Organophosphorus Chemistry, Marcel Dekker, New York, 1992, Chapter 10; L.D. Quin, in: A. Katritzky, C. Rees, W.E.F.V. Scriven (Eds.), Comprehensive Heterocyclic Chemistry, Vol. 2, Pergamon, Oxford, England, 1996, Vol. 2, pp. 757-856. Aromaticity indices of different type are much smaller for phosphole than for other five membered rings; K.K. Baldridge, M.S. Gordon, J. Am. Chem. Soc. 110 (1988) 4204; L. Nyulászi, T. Veszprémi, J. Réffy, B. Burkhardt, M. Regitz, J. Am. Chem. Soc. 114 (1992) 9080; V.I. Minkin, M.N. Glukhotsev, B.Ya. Simkin, Aromaticity and Antiaromaticity - Electronic and Structural Aspects, Wiley, New York, 1994; P.v.R. Schleyer, P.K. Freeman, H. Jiao, B. Goldfuss, Angew. Chem. Int. Ed. Engl. 34 (1995) 337.
    • (1992) J. Am. Chem. Soc. , vol.114 , pp. 9080
    • Nyulászi, L.1    Veszprémi, T.2    Réffy, J.3    Burkhardt, B.4    Regitz, M.5
  • 6
    • 0004142484 scopus 로고
    • Wiley, New York
    • For comprehensive works see: F. Mathey, Chem. Rev. 88 (1988) 437; A.N. Hughes, in: R. Engel (Ed.), Handbook of Organophosphorus Chemistry, Marcel Dekker, New York, 1992, Chapter 10; L.D. Quin, in: A. Katritzky, C. Rees, W.E.F.V. Scriven (Eds.), Comprehensive Heterocyclic Chemistry, Vol. 2, Pergamon, Oxford, England, 1996, Vol. 2, pp. 757-856. Aromaticity indices of different type are much smaller for phosphole than for other five membered rings; K.K. Baldridge, M.S. Gordon, J. Am. Chem. Soc. 110 (1988) 4204; L. Nyulászi, T. Veszprémi, J. Réffy, B. Burkhardt, M. Regitz, J. Am. Chem. Soc. 114 (1992) 9080; V.I. Minkin, M.N. Glukhotsev, B.Ya. Simkin, Aromaticity and Antiaromaticity - Electronic and Structural Aspects, Wiley, New York, 1994; P.v.R. Schleyer, P.K. Freeman, H. Jiao, B. Goldfuss, Angew. Chem. Int. Ed. Engl. 34 (1995) 337.
    • (1994) Aromaticity and Antiaromaticity - Electronic and Structural Aspects
    • Minkin, V.I.1    Glukhotsev, M.N.2    Simkin, B.ya.3
  • 7
    • 33748247829 scopus 로고
    • For comprehensive works see: F. Mathey, Chem. Rev. 88 (1988) 437; A.N. Hughes, in: R. Engel (Ed.), Handbook of Organophosphorus Chemistry, Marcel Dekker, New York, 1992, Chapter 10; L.D. Quin, in: A. Katritzky, C. Rees, W.E.F.V. Scriven (Eds.), Comprehensive Heterocyclic Chemistry, Vol. 2, Pergamon, Oxford, England, 1996, Vol. 2, pp. 757-856. Aromaticity indices of different type are much smaller for phosphole than for other five membered rings; K.K. Baldridge, M.S. Gordon, J. Am. Chem. Soc. 110 (1988) 4204; L. Nyulászi, T. Veszprémi, J. Réffy, B. Burkhardt, M. Regitz, J. Am. Chem. Soc. 114 (1992) 9080; V.I. Minkin, M.N. Glukhotsev, B.Ya. Simkin, Aromaticity and Antiaromaticity - Electronic and Structural Aspects, Wiley, New York, 1994; P.v.R. Schleyer, P.K. Freeman, H. Jiao, B. Goldfuss, Angew. Chem. Int. Ed. Engl. 34 (1995) 337.
    • (1995) Angew. Chem. Int. Ed. Engl. , vol.34 , pp. 337
    • Schleyer, P.V.R.1    Freeman, P.K.2    Jiao, H.3    Goldfuss, B.4
  • 30
    • 0003484909 scopus 로고
    • Caos/CAMM Center Nijmegen, The Netherlands
    • G. Schaftenaar, MOLDEN 2.5; Caos/CAMM Center Nijmegen, The Netherlands, 1994.
    • (1994) MOLDEN 2.5;
    • Schaftenaar, G.1
  • 32
    • 0040674453 scopus 로고    scopus 로고
    • It is known that conjugative/aromatic stabilization effects are somewhat underestimated at the HF (while are overestimated at the MP2) level (see e.g. ref. [9]).This results in a reduction of aromaticity indices, when calculated from data obtained at the HF level. The underestimation of the aromatic stabilization at the HF level becomes apparent at larger OOP angles. Lacking (a part of) such a stabilization by using the HF procedure the optimized geometry is less planar than for the real structure. Also in case of 6′ the phenyl ring is somewhat distorted from the symmetry plane of the phosphole ring, while in the X-ray structure of 6 this distortion is negligibly small. The distorted phenyl ring has a smaller steric repulsion than the symmetric one.
    • It is known that conjugative/aromatic stabilization effects are somewhat underestimated at the HF (while are overestimated at the MP2) level (see e.g. ref. [9]).This results in a reduction of aromaticity indices, when calculated from data obtained at the HF level. The underestimation of the aromatic stabilization at the HF level becomes apparent at larger OOP angles. Lacking (a part of) such a stabilization by using the HF procedure the optimized geometry is less planar than for the real structure. Also in case of 6′ the phenyl ring is somewhat distorted from the symmetry plane of the phosphole ring, while in the X-ray structure of 6 this distortion is negligibly small. The distorted phenyl ring has a smaller steric repulsion than the symmetric one.


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