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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.
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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.
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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.
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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.
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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.
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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.
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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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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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