Skip to content
BY-NC-ND 3.0 license Open Access Published by De Gruyter Open Access March 1, 2004

Aromatic heterocycles XII. Semiempirical PM3 study of Diels-Alder cycloaddition reaction of substituted phosphabenzenes

Liliana Pacureanu, Mircea Mracec and Zeno Simon
From the journal Open Chemistry

Abstract

We report the results of a semiempirical PM3 study of the 1,4 cycloaddition reaction of substituted λ3-phosphabenzenes with alkynes. The influence of the nature, position and steric hindrance of substituents on the reaction energy is studied. Except for some values, the results are in reasonable agreement with experimental observations and electronic effects of substituents.

[1] C. Elschenbroich, M. Nowotny, A. Behrendt, K. Harms, S. Wocadlo and J. Pebler: “Pentakis (η 1-phosphinine)iron: synthesis, structure and mode of formation”, J. Am. Chem. Soc., Vol. 116, (1994), pp. 6217–6219. http://dx.doi.org/10.1021/ja00093a02210.1021/ja00093a022Search in Google Scholar

[2] A.J. Ashe III and J.C. Colburn: “Molybdenum-Carbonyl Complexes of the Group 5 Heterobenzenes”, J. Am. Chem. Soc., Vol. 99, (1977), pp. 8099–8100. http://dx.doi.org/10.1021/ja00466a07810.1021/ja00466a078Search in Google Scholar

[3] C. Elschenbroich, J. Koch, J. Kroker, M. Winsch, W. Massa, G. Baum and G. Stork: “η 6-Coordination von unsubstituierten pyridine η 6-benzol(η 6-pyridin) chrom und bis(η 6-pyridin)chrom”, Chem. Ber., Vol. 121, (1988), pp. 1983. Search in Google Scholar

[4] K. Dimroth, R. Thamm und H. Kaletsch: “6π-Komplexe von pyridine-derivaten, synthesen und reactionen”, Z. Naturforsch., Vol. 39b, (1984), pp. 207–212. Search in Google Scholar

[5] P. Rosa, N. Mezailles, L. Ricard, F. Mathey, P. Le Floch, and Y. Jean: “Dianionic Iron and Ruthenium(2-) Biophosphinine Complexes: A Formal d10 Ruthenium Complex”, Angew. Chem. Int. Ed. Engl., Vol. 40, (2001), pp. 1251–1255. http://dx.doi.org/10.1002/1521-3773(20010401)40:7<1251::AID-ANIE1251>3.0.CO;2-H10.1002/1521-3773(20010401)40:7<1251::AID-ANIE1251>3.0.CO;2-HSearch in Google Scholar

[6] P. Le Floch and F. Mathey: “Transition Metals in Phosphinine Chemistry”, Coord. Chem. Rev., Vol. 179–180, (1998), pp. 771–791. Search in Google Scholar

[7] C. Elschenbroich, S. Voss, O. Schiemann, A. Lippek and K. Harms: “η 1-Coordination of phosphinine to chromium, molybdenum and tungsten”, Organometallics, Vol. 17, (1998), pp. 4417–4424. http://dx.doi.org/10.1021/om980487910.1021/om9804879Search in Google Scholar

[8] C. Elschenbroich, M. Nowotny, A. Behrendt, W. Massa, S. Wocadlo: “Tetrakis(η 1 phosphabenzene)nikel”, Angew. Chem. Int. Ed. Engl. Vol. 31, (1992), pp. 1343–1345. http://dx.doi.org/10.1002/anie.19921343110.1002/anie.199213431Search in Google Scholar

[9] M. Mracec, M. Mracec, and Z. Simon: “X Aromatic Heterocycles. PM3 and HMO Study on the Diels-Alder Reactions of λ3-Heterobenzenes of The 15th Group”, Revue Roumaine de Chimie, Vol.45, (2000), pp. 1021–1025. Search in Google Scholar

[10] C. Batich, E. Heilbronner, V. Hornung, A.J. Ashe III, D.T. Clark, K.T. Cobley, D. Kilcast and I. Scanlan: “Photoelectron spectra of Phosphabenzene, Arsabenzene and Stibabenzene”, J. Am. Chem. Soc., Vol. 95, (1973), pp. 928. http://dx.doi.org/10.1021/ja00784a05410.1021/ja00784a054Search in Google Scholar

[11] A.J. Ashe III: “The group V heterobenzenes”, Acc. Chem. Res., Vol. 11, (1978), pp. 153. http://dx.doi.org/10.1021/ar50124a00510.1021/ar50124a005Search in Google Scholar

[12] G. Märkl and A. Merz: “Zur unsetzung des phosphabenzolsystem mit carbenen und carbenoiden”, Tetrahedron Letter, (1971), pp. 1269–1273. Search in Google Scholar

[13] L. Nyulaszi and G. Keglevich: “Study on the aromaticity and reactivity of chlorophosphinine”, Heteroat. Chem., Vol. 5, (1994), pp. 131–137. http://dx.doi.org/10.1002/hc.52005020910.1002/hc.520050209Search in Google Scholar

[14] G. Frisson, A. Sevin, N. Avarvari, F. Mathey and P. Le Floch: “The CH by N replacement effects on the aromaticity and reactivity of phosphinines”, J. Org. Chem., Vol. 64, (1999), pp. 5524–5529. http://dx.doi.org/10.1021/jo990361110.1021/jo9903611Search in Google Scholar

[15] H. Oehling, W. Schäfer and A. Schweig: “Sequence of highest occupied molecular orbital in the phosphorins system”, Angew. Chem.Int.Ed.Engl., Vol. 10, (1971), pp. 656–657. http://dx.doi.org/10.1002/anie.19710656110.1002/anie.197106561Search in Google Scholar

[16] G. Märkl: “2,4,6-Triphenylphosphabenzol”, Angew. Chem., Vol. 78, (1966), pp. 907. Search in Google Scholar

[17] K. Dimroth: Phosphorus Carbon Double Bonds, Springer-Verlag, Berlin, 1973. http://dx.doi.org/10.1007/BFb005136510.1007/BFb0051365Search in Google Scholar

[18] G. Märkl: “Phosphabenzol uns arsabenzol”, Chem. Unserer Zeit, Vol. 16, (1982), pp. 1939. http://dx.doi.org/10.1002/ciuz.1982016050310.1002/ciuz.19820160503Search in Google Scholar

[19] G. Märkl: “Aromatic Phosphorus Heterocycles”, Phosphorus and Sulfur, Vol. 3, (1977), pp. 77. Search in Google Scholar

[20] A.J.III Ashe and M.D. Gordon: “Bismabenzene. Diels-Alder Reaction of Group V Heteroaromatic with Hexafluorobutyne”, J. Amer. Chem. Soc., Vol. 94, (1972), pp. 7596. http://dx.doi.org/10.1021/ja00776a06310.1021/ja00776a063Search in Google Scholar

[21] G. Märkl and F. Lieb: “Substituierte 1-Phosphaberrelenes”, Angew. Chem., Vol. 80, (1968), pp. 702. Search in Google Scholar

[22] M. Alcaraz and F. Mathey: “Accroisment de la reactivite des phosphorines en tant que dienes et philodienes par complexation du phosphore”, Tetrahedron, Vol. 25, (1984), pp. 207. http://dx.doi.org/10.1016/S0040-4039(00)99841-110.1016/S0040-4039(00)99841-1Search in Google Scholar

[23] R. Stutmann: “A simple model for substituent effects in cycloaddition reaction”, Tetrahedron Lett., Vol. 29, (1971), pp. 2721–2724. http://dx.doi.org/10.1016/S0040-4039(01)96962-X10.1016/S0040-4039(01)96962-XSearch in Google Scholar

[24] G. Märkl, F. Lieb and C. Martin: “Substituierte benzo-phosphabarrelenes zur umsetzung von phosphabenzolen mit arinen”, Tetrahedron Lett, Vol. 13, (1971), pp. 1249. http://dx.doi.org/10.1016/S0040-4039(01)96678-X10.1016/S0040-4039(01)96678-XSearch in Google Scholar

[25] R.B. Woodward and R. Hoffmann: The conservation of orbital symmetry, Chemie Verlag, Weinheim, 1970. 10.1016/B978-1-4832-3290-4.50006-4Search in Google Scholar

[26] R. Hoffmann, R.B. Woodward: “Selection rules for concerted cycloaddition reaction”, J. Am. Chem. Soc., Vol. 87, (1965), pp. 2046–2048. http://dx.doi.org/10.1021/ja01087a03410.1021/ja01087a034Search in Google Scholar

[27] Hyper Chem Professional for Windows, Release 5.11, Hypercube Inc., Gainesville, Fl. 32601, USA, 1997. Search in Google Scholar

[28] M.J.S. Dewar, E.G. Zoldbush, E.F. Haley and J.J.P. Steward: “AM1, a new general purpose quantum mechanical molecular model”, J. Am. Chem. Soc., Vol. 107, (1985), pp. 3902–3909. http://dx.doi.org/10.1021/ja00299a02410.1021/ja00299a024Search in Google Scholar

Published Online: 2004-3-1
Published in Print: 2004-3-1

© 2004 Versita Warsaw

This work is licensed under the Creative Commons Attribution-NonCommercial-NoDerivatives 3.0 License.

Scroll Up Arrow