Catenation of two singlet diradicals: Synthesis of a stable tetraradical (tetraradicaloid)

Angewandte Chemie - International Edition

Volumn 43, Issue 37, 2004, Pages 4876-4880

  Rodriguez, Amor ^a   Tham, Fook S ^a   Schoeller, Wolfgang W ^b   Bertrand, Guy ^a  

^a UNIVERSITY OF CALIFORNIA   (United States)

^b BIELEFELD UNIVERSITY   (Germany)

Author keywords

Born; Magnetic properties; Phosphorus; Radicals

Indexed keywords

ANTIFERROMAGNETIC MATERIALS; AROMATIC COMPOUNDS; ISOMERS; SYNTHESIS (CHEMICAL);

ANTIFERROMAGNETIC LINKERS; BICYCLIC ISOMERS; CATENATION; ENERGY DIFFERENCE;

FREE RADICALS;

RADICAL;

ARTICLE; CALORIE; ENERGY; REACTION ANALYSIS; SOLID STATE; SYNTHESIS;

EID: 4744356127     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200460473     Document Type: Article

References (51)

1. a) J. A. Berson in Reactive Intermediate Chemistry (Eds.: R. A. Moss, M. S. Platz, M. Jones, Jr.), Wiley-Interscience, Hoboken, NJ, 2004, pp. 165-204;
2. b) W.T. Borden in Encyclopedia of Computational Chemistry (Ed.: P. v. R. Schleyer), Wiley, New York, 1998, pp. 708-722;
3. c) J. A. Berson, Acc. Chem. Res. 1997, 30, 238;
4. d) D. A. Dougherty, Acc. Chem. Res. 1991, 24, 88.
5. Conjugated Polymers and Related Material (Eds.: W. R. Salaneck, L. Lundstrom, B. Ranby), Oxford, New York, 1993.
6. H. S. M. Lu, J. A. Berson, J. Am. Chem. Soc. 1997, 119, 1428; H. S. M. Lu, J. A. Berson, J. Am. Chem. Soc. 1996, 118, 265.
7. H. S. M. Lu, J. A. Berson, J. Am. Chem. Soc. 1997, 119, 1428; H. S. M. Lu, J. A. Berson, J. Am. Chem. Soc. 1996, 118, 265.
8. For recent work on carbon-based 1,3-diradicals: a) A. C. Goren, D. A. Hrovat, M. Seefelder, H. Quast, W. T. Borden, J. Am. Chem. Soc. 2002, 124, 3469;
9. b) M. Abe, W. Adam, T. Minamoto, Y. Ino, M. Nojima, J. Org. Chem. 2003, 68, 1796;
10. c) M. Abe, W. Adam, W. T. Borden, M. Hattori, D. A. Hrovat, M. Nojima, K. Nozaki, J. Wirz, J. Am. Chem. Soc. 2004, 126, 574.
11. Several heterocyclobutane-1,3-diyls that contain Group 14 and/or Group 15 elements confined by a trans-annular antibonding π-overlap, which makes the thermal ring closure forbidden have been isolated: a) E. Niecke, A. Fuchs, F. Baumeister, M. Nieger, W. W. Schoeller, Angew. Chem. 1995, 107, 640; Angew. Chem. Int. Ed. Engl. 1995, 34, 555;
12. Several heterocyclobutane-1,3-diyls that contain Group 14 and/or Group 15 elements confined by a trans-annular antibonding π-overlap, which makes the thermal ring closure forbidden have been isolated: a) E. Niecke, A. Fuchs, F. Baumeister, M. Nieger, W. W. Schoeller, Angew. Chem. 1995, 107, 640; Angew. Chem. Int. Ed. Engl. 1995, 34, 555;
13. b) 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;
14. b) 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. c) E. Niecke, A. Fuchs, M. Nieger, Angew. Chem. 1999, 111, 3213; Angew. Chem. Int. Ed. 1999, 38, 3028;
16. c) E. Niecke, A. Fuchs, M. Nieger, Angew. Chem. 1999, 111, 3213; Angew. Chem. Int. Ed. 1999, 38, 3028;
17. d) W. W. Schoeller, C. Begemann, E. Niecke, D. Gudat, J. Phys. Chem. A 2001, 105, 10731;
18. e) H. Sugiyama, S. Ito, M. Yoshifuji, Angew. Chem. 2003, 115, 3932; Angew. Chem. Int. Ed. 2003, 42, 3802;
19. e) H. Sugiyama, S. Ito, M. Yoshifuji, Angew. Chem. 2003, 115, 3932; Angew. Chem. Int. Ed. 2003, 42, 3802;
20. f) M. Sebastian, M. Nieger, D. Szieberth, L. Nyulaszi, E. Niecke, Angew. Chem. 2004, 116, 647; Angew. Chem. Int. Ed. 2004, 43, 637;
21. f) M. Sebastian, M. Nieger, D. Szieberth, L. Nyulaszi, E. Niecke, Angew. Chem. 2004, 116, 647; Angew. Chem. Int. Ed. 2004, 43, 637;
22. g) C. Cui, P. P. Power, Abstr. Am. Chem. Soc. Meet. 2004, 801;
23. h) M. F. Lappert, Abstr. Am. Chem. Soc. Meet. 2004, 427.
24. For reviews on diradicals based on main group elements see: a) H. Grützmacher, F. Breher, Angew. Chem. 2002, 114, 4178; Angew. Chem. Int. Ed. 2002, 41, 4006;
25. For reviews on diradicals based on main group elements see: a) H. Grützmacher, F. Breher, Angew. Chem. 2002, 114, 4178; Angew. Chem. Int. Ed. 2002, 41, 4006;
26. b) P. P. Power, Chem. Rev. 2003, 103, 789.
27. D. Scheschkewitz, H. Amii, H. Gornitzka, W. W. Schoeller, D. Bourissou, G. Bertrand, Angew. Chem. 2004, 116, 595; Angew. Chem. Int. Ed. 2004, 43, 585.
28. D. Scheschkewitz, H. Amii, H. Gornitzka, W. W. Schoeller, D. Bourissou, G. Bertrand, Angew. Chem. 2004, 116, 595; Angew. Chem. Int. Ed. 2004, 43, 585.
29. For discussions on the diradical character of derivatives of type A: a) M. Seierstad, C. R. Kinsinger, C. J. Cramer, Angew. Chem. 2002, 114, 4050; Angew. Chem. Int. Ed. 2002, 41, 3894;
30. For discussions on the diradical character of derivatives of type A: a) M. Seierstad, C. R. Kinsinger, C. J. Cramer, Angew. Chem. 2002, 114, 4050; Angew. Chem. Int. Ed. 2002, 41, 3894;
31. b) W. W. Schoeller, A. Rozhenko, D. Bourissou, G. Bertrand, Chem. Eur. J. 2003, 9, 3611;
32. c) Y. Jung, M. Head-Gordon, J. Phys. Chem. A 2003, 107, 7475;
33. d) M. J. Cheng, C. H. Hu, Mol. Phys. 2003, 101, 1319.
34. a) D. Scheschkewitz, H. Amii, H. Gornitzka, W. W. Schoeller, D. Bourissou, G. Bertrand, Science 2002, 295, 1880;
35. b) H. Amii, L. Vranicar, H. Gornitzka, D. Bourissou, G. Bertrand, J. Am. Chem. Soc. 2004, 126, 1344.
36. a) A. Rajca, Chem. Rev. 1994, 94, 871;
37. b) C. Rovira, D. Ruiz-Molina, O. Elsner, J. Vidal-Gancedo, J. Bonvoisin, J. P. Launay, J. Veciana, Chem. Eur. J. 2001, 7, 240.
38. 1,2-diphenyl-1,2-dichloro-diborane is known to be highly unstable: H. Hommer, H. Nöth, J. Knizek, W. Ponikwar, H. Schwenk-Kircher, Eur. J. Inorg. Chem. 1998, 1519.
39. As observed for related carbon-based singlet 1,3-diradicals,[4] derivatives of type A are strongly colored, whereas the bicyclic[1.1.0] isomers B are colorless.
40. 3, CCDC-236922 (p-4) and 236923 (m-4) contain the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/conts/ retrieving.html (or from the Cambridge Crystallographic Data Centre, 12, Union Road, Cambridge CB21EZ, UK; fax: (+44)1223-336-033; or deposit@ ccdc.cam.ac.uk).
41. A. Rodriguez, R. A. Olsen, N. Ghaderi, D. Scheschkewitz, F. S. Tham, L. J. Mueller, G. Bertrand, Angew. Chem. 2004,116, DOI: 10.1002/ange.200460475; Angew. Chem. Int. Ed. 2004, 43, DOI: 10.1002/anie.200460475.
42. A. Rodriguez, R. A. Olsen, N. Ghaderi, D. Scheschkewitz, F. S. Tham, L. J. Mueller, G. Bertrand, Angew. Chem. 2004,116, DOI: 10.1002/ange.200460475; Angew. Chem. Int. Ed. 2004, 43, DOI: 10.1002/anie.200460475.
43. A fully quinoid stucture, in which the unpaired electrons are located far to each other, is expected for the related parabis(cyclobutanediyl)phenyl system. Consequently, CAS(4,4)/6-31g* calculations result in a singlet-triplet energy separation equal to zero.
44. Gaussian 98 (Revision A.7), M.J. Frisch, G.W. Trucks, H.B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, V. G. Zakrzewski, J. A. Montgomery, R. E. Stratmann, J. C. Burant, S. Dapprich, J. M. Millam, A. D. Daniels, K. N. Kudin, M. C. Strain, O. Farkas, J. Tomasi, V. Barone, M. Cossi, R. Cammi, B. Mennucci, C. Pomelli, C. Adamo, S. Clifford, J. Ochterski, G. A. Petersson, P. Y. Ayala, Q. Cui, K. Morokuma, D. K. Malick, A. D. Rabuck, K. Raghavachari, J. B. Foresman, J. Cioslowski, J. V. Ortiz, B. B. Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R. Gomperts, R. L. Martin, D. J. Fox, T. Keith, M. A. Al-Laham, C. Y. Peng, A. Nanayakkara, C. Gonzalez, M. Challacombe, P. M. W. Gill, B. G. Johnson, W. Chen, M. W. Wong, J. L. Andres, M. Head-Gordon, E. S. Replogle, J. A. Pople, Gaussian, Inc., Pittsburgh, PA, 1998.
45. a) A. Berndt, Angew. Chem. 1993, 105, 1034; Angew. Chem. Int. Ed. Engl. 1993, 32, 985;
46. a) A. Berndt, Angew. Chem. 1993, 105, 1034; Angew. Chem. Int. Ed. Engl. 1993, 32, 985;
47. b) R. Boese, P. Paetzold, A. tapper, R. Ziembinski, Chem. Ber. 1989, 122, 1057.
48. No evidence for the existence of the unsymmetrical compound featuring a bicyclic and a four-membered-ring unit has been found. Moreover, the equilibrium between p-4A and p-4B is not solvent dependent.
49. a) SMART Software Reference Manual, Version 5.054, Bruker Analytical X-ray System, Inc., Madison, WI 1997-1998;
50. b) SAINTPLUS Software Reference Manual, Version 6.02A, Bruker Analytical X-Ray System, Inc., Madison, WI 1997-1998;
51. th, Bruker Analytical X-ray System, Inc., Madison, WI, 2000.