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

• Authors: Liliana Pacureanu , Mircea Mracec , Zeno Simon
• Languages of publication: EN

Abstracts

EN

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.

Keywords

EN

Diels-Alder cycloaddition reaction; λ3-phosphabenzene ; 1-phosphabarrelene; semiempirical PM3 method

• Publisher: De Gruyter Open
• Journal: Open Chemistry
• Year: 2004
• Volume: 2
• Issue: 1
• Pages: 34-51

Dates

published

1 - 3 - 2004

online

1 - 3 - 2004

Contributors

author

Liliana Pacureanu

• Institute of Chemistry of Romanian Academy, 24 Mihai Viteazul Avenue, 300223, Timisoara, Romania

author

Mircea Mracec

• Institute of Chemistry of Romanian Academy, 24 Mihai Viteazul Avenue, 300223, Timisoara, Romania

author

Zeno Simon

• Institute of Chemistry of Romanian Academy, 24 Mihai Viteazul Avenue, 300223, Timisoara, Romania

References

• [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/ja00093a022[Crossref]
• [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/ja00466a078[Crossref]
• [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.
• [4] K. Dimroth, R. Thamm und H. Kaletsch: “6π-Komplexe von pyridine-derivaten, synthesen und reactionen”, Z. Naturforsch., Vol. 39b, (1984), pp. 207–212.
• [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-H[Crossref]
• [6] P. Le Floch and F. Mathey: “Transition Metals in Phosphinine Chemistry”, Coord. Chem. Rev., Vol. 179–180, (1998), pp. 771–791.
• [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/om9804879[Crossref]
• [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.199213431[Crossref]
• [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.
• [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/ja00784a054[Crossref]
• [11] A.J. Ashe III: “The group V heterobenzenes”, Acc. Chem. Res., Vol. 11, (1978), pp. 153. http://dx.doi.org/10.1021/ar50124a005[Crossref]
• [12] G. Märkl and A. Merz: “Zur unsetzung des phosphabenzolsystem mit carbenen und carbenoiden”, Tetrahedron Letter, (1971), pp. 1269–1273.
• [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.520050209[Crossref]
• [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/jo9903611[Crossref]
• [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.197106561[Crossref]
• [16] G. Märkl: “2,4,6-Triphenylphosphabenzol”, Angew. Chem., Vol. 78, (1966), pp. 907.
• [17] K. Dimroth: Phosphorus Carbon Double Bonds, Springer-Verlag, Berlin, 1973. http://dx.doi.org/10.1007/BFb0051365[Crossref]
• [18] G. Märkl: “Phosphabenzol uns arsabenzol”, Chem. Unserer Zeit, Vol. 16, (1982), pp. 1939. http://dx.doi.org/10.1002/ciuz.19820160503[Crossref]
• [19] G. Märkl: “Aromatic Phosphorus Heterocycles”, Phosphorus and Sulfur, Vol. 3, (1977), pp. 77.
• [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/ja00776a063[Crossref]
• [21] G. Märkl and F. Lieb: “Substituierte 1-Phosphaberrelenes”, Angew. Chem., Vol. 80, (1968), pp. 702.
• [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)99841-1[Crossref]
• [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-X[Crossref]
• [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-X[Crossref]
• [25] R.B. Woodward and R. Hoffmann: The conservation of orbital symmetry, Chemie Verlag, Weinheim, 1970.
• [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/ja01087a034[Crossref]
• [27] Hyper Chem Professional for Windows, Release 5.11, Hypercube Inc., Gainesville, Fl. 32601, USA, 1997.
• [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/ja00299a024[Crossref]

Identifiers

DOI

10.2478/BF02476183