Valence isomerization of a 1,3-diphosphacyclobutane-2,4-diyl: Photochemical ring closure to 2,4-diphosphabicyclo[1.1.0]butane and its thermal ring opening to gauche-1,4-diphosphabutadiene

Angewandte Chemie - International Edition

Volumn 38, Issue 20, 1999, Pages 3028-3031

  Niecke, Edgar ^a   Fuchs, André ^a   Nieger, Martin ^a  

^a UNIVERSITY OF BONN   (Germany)

Author keywords

Bond stretch isomers; Phosphaalkenes; Phosphorus heterocycles; Valence isomerization

Indexed keywords

ALKENE DERIVATIVE; CYCLOBUTANE DERIVATIVE;

ARTICLE; CARBON NUCLEAR MAGNETIC RESONANCE; CHEMICAL ANALYSIS; CHEMICAL MODIFICATION; CRYSTAL STRUCTURE; ISOMERISM; PHOSPHORUS NUCLEAR MAGNETIC RESONANCE; PHOTOCHEMISTRY; STRUCTURE ANALYSIS; SYNTHESIS;

EID: 0033581582     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/(SICI)1521-3773(19991018)38:20<3028::AID-ANIE3028>3.0.CO;2-D     Document Type: Article

References (27)

1. 2 see: a) J. Bragin, M. V. Evans, J. Chem. Phys. 1969, 57, 268; b) A. J. Banister, Phosphorus Sulfur 1979, 6,421; c) A. A. Bhattacharyya, A. Bhattacharyya, R. R. Adkins, A. G. Turner, J. Am. Chem. Soc. 1981, 103, 7458; d) G. van Zandwijk, R. A. J. Jansen, H. M. Buck, J. Am. Chem. Soc. 1990, 112, 4155; e) R. A. J. Janssen, J. Phys. Chem. 1993, 97, 6384.
2. 2 see: a) J. Bragin, M. V. Evans, J. Chem. Phys. 1969, 57, 268; b) A. J. Banister, Phosphorus Sulfur 1979, 6,421; c) A. A. Bhattacharyya, A. Bhattacharyya, R. R. Adkins, A. G. Turner, J. Am. Chem. Soc. 1981, 103, 7458; d) G. van Zandwijk, R. A. J. Jansen, H. M. Buck, J. Am. Chem. Soc. 1990, 112, 4155; e) R. A. J. Janssen, J. Phys. Chem. 1993, 97, 6384.
3. 2 see: a) J. Bragin, M. V. Evans, J. Chem. Phys. 1969, 57, 268; b) A. J. Banister, Phosphorus Sulfur 1979, 6,421; c) A. A. Bhattacharyya, A. Bhattacharyya, R. R. Adkins, A. G. Turner, J. Am. Chem. Soc. 1981, 103, 7458; d) G. van Zandwijk, R. A. J. Jansen, H. M. Buck, J. Am. Chem. Soc. 1990, 112, 4155; e) R. A. J. Janssen, J. Phys. Chem. 1993, 97, 6384.
4. 2 see: a) J. Bragin, M. V. Evans, J. Chem. Phys. 1969, 57, 268; b) A. J. Banister, Phosphorus Sulfur 1979, 6,421; c) A. A. Bhattacharyya, A. Bhattacharyya, R. R. Adkins, A. G. Turner, J. Am. Chem. Soc. 1981, 103, 7458; d) G. van Zandwijk, R. A. J. Jansen, H. M. Buck, J. Am. Chem. Soc. 1990, 112, 4155; e) R. A. J. Janssen, J. Phys. Chem. 1993, 97, 6384.
5. 2 see: a) J. Bragin, M. V. Evans, J. Chem. Phys. 1969, 57, 268; b) A. J. Banister, Phosphorus Sulfur 1979, 6,421; c) A. A. Bhattacharyya, A. Bhattacharyya, R. R. Adkins, A. G. Turner, J. Am. Chem. Soc. 1981, 103, 7458; d) G. van Zandwijk, R. A. J. Jansen, H. M. Buck, J. Am. Chem. Soc. 1990, 112, 4155; e) R. A. J. Janssen, J. Phys. Chem. 1993, 97, 6384.
6. C. M. Mikulski, P. J. Russo, M. S. Saran, A. G. MacDiarmid, A. F. Garito, A. J. Haeger, J. Am. Chem. Soc. 1975, 97, 6358, and references therein.
7. E. Niecke, A. Fuchs, F. Baumeister, M. Nieger, W. W. Schoeller, Angew. Chem. 1995, 107, 640; Angew. Chem. Int. Ed. Engl. 1995, 34, 555.
8. E. Niecke, A. Fuchs, F. Baumeister, M. Nieger, W. W. Schoeller, Angew. Chem. 1995, 107, 640; Angew. Chem. Int. Ed. Engl. 1995, 34, 555.
9. For the term "bond stretch isomer" see : W.-D. Stohrer, R. Hoffmann, J. Am. Chem. Soc. 1972, 94, 779.
10. E. Niecke, M. Nieger, A. Fuchs, O. Schmidt, unpublished results
11. 2: R. D. Harcourt, T. M. Klapötke, A. Schulz, P. Wolynec, J. Phys. Chem. 1998, 102, 1850.
12. -1. [5, 10]
13. According to the Woodward - Hoffmann rules, a 2,4-connection in 1,3-diphosphetane-2,4-diyl is a forbidden process.
14. O. Schmidt, A. Fuchs, D. Gudat, M. Nieger, W. Hoffbauer, E. Niecke, W. W. Schoeller, Angew. Chem. 1998, 110, 995 ; Angew. Chem. Int. Ed. 1998, 37, 949.
15. O. Schmidt, A. Fuchs, D. Gudat, M. Nieger, W. Hoffbauer, E. Niecke, W. W. Schoeller, Angew. Chem. 1998, 110, 995 ; Angew. Chem. Int. Ed. 1998, 37, 949.
16. Stable phosphanylcarbenes are known: A. Igau, H. Grützmacher, A. Baceiredo, G. Bertrand, J. Am. Chem. Soc. 1988, 110, 6463.
17. 1,2- and 1,3-diphosphabicyclo[1.1.0]butanes are known: E. Niecke, H. J. Metternich, R. Streubel, Chem. Ber. 1990, 123, 67.
18. Transition metal complexes of cis-1,4-diphosphabutadienes are known: P. Le Floch, N. Maigrot, L. Ricard, C. Charrier, F. Mathey, Inorg. Chem. 1995, 34, 5070.
19. Short heating to 150 C leads to no significant change in the compound.
20. C. Charrier, N. Maigrot, F. Mathey, F. Robert, Y. Jeannin, Organometallics 1986, 5, 623.
21. 2) was 0.107 with a conventional R(F) = 0.039 for 397 parameters. Crystallographic data (excluding structure factors) for the structures reported in this paper have been deposited with the Cambridge Crystallographic Data Centre as supplementary publication nos. CCDC-112271 (3), 112272 (4), and 112273 (5). Copies of the data can he obtained free of charge on application to CCDC, 12 Union Road, Cambridge CB21EZ, UK (fax: ( + 44) 1223-336-033; e-mail: deposit@ccdc.cam.ac.uk).
22. G. M. Sheldrick, SHELXS-97, Acta Crystallogr. Sect. A 1990, 46, 467.
23. G. M. Sheldrick, SHELXL-97, Universität Göttingen, 1997.
24. R. Appel in Multiple Bonding and Low Coordination in Phosphorus Chemistry (Eds.: M. Regitz, O. J. Scherer), Thieme, 1990, p. 367.
25. The cis form does not represent a minimum on the energy hypersur- face : a) W. W. Schoeller, U. Tubbesing, A. B. Rozhenko, Eur. J. Inorg. Chem. 1998, 951; b) S. M. Bachrach, M. Liu, J. Org. Chem. 1992, 57, 2040.
26. The cis form does not represent a minimum on the energy hypersur- face : a) W. W. Schoeller, U. Tubbesing, A. B. Rozhenko, Eur. J. Inorg. Chem. 1998, 951; b) S. M. Bachrach, M. Liu, J. Org. Chem. 1992, 57, 2040.
27. K. A. Nguyen, M. S. Gordon, J. Am. Chem. Soc. 1995, 117, 385.