Borylated methylenephosphonium salts: Precursors of elusive boryl(phosphino)carbenes

Journal of the American Chemical Society

Volumn 132, Issue 26, 2010, Pages 8864-8865

  Lavigne, Florie ^a   Maerten, Eddy ^a   Alcaraz, Gilles ^b   Saffon Merceron, Nathalie ^c   Acosta Silva, Carles ^d   Branchadell, Vicenç ^d   Baceiredo, Antoine ^a  

^a UNIVERSITÉ PAUL SABATIER   (France)

^b LCC LABORATOIRE DE CHIMIE DE COORDINATION   (France)

^c Université Paul Sabatier   (France)

^d UNIVERSITAT AUTÒNOMA DE BARCELONA   (Spain)

Author keywords

[No Author keywords available]

Indexed keywords

CARBENES; DENSITY FUNCTIONAL THEORY CALCULATIONS; IMINIUM SALTS; NMR SPECTROSCOPY; SINGLET-TRIPLET ENERGY GAP;

NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; ORGANIC POLYMERS; PHOSPHORUS; SALTS; X RAY CRYSTALLOGRAPHY;

DENSITY FUNCTIONAL THEORY;

CARBENE; PHOSPHONIUM DERIVATIVE;

ARTICLE; CALCULATION; DENSITY FUNCTIONAL THEORY; ENERGY; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; PRECURSOR; SYNTHESIS; X RAY CRYSTALLOGRAPHY;

EID: 77954300313     PISSN: 00027863     EISSN: 15205126     Source Type: Journal    
DOI: 10.1021/ja103422b     Document Type: Article

References (29)

1. Igau, A., Grutzmacher, H., Baceiredo, A., and Bertrand, G. J. Am. Chem. Soc. 1988, 110, 6463
2. Arduengo, A. J., Harlow, R. L., and Kline, M. J. Am. Chem. Soc. 1991, 113, 361
3. Bourissou, D., Guerret, O., Gabbai, F. P., and Bertrand, G. Chem. Rev. 2000, 100, 39
4. Canac, Y., Soleilhavoup, M., Conejero, S., and Bertrand, G. J. Organomet. Chem. 2004, 689, 3857
5. Vignolle, J., Cattoën, X., and Bourissou, D. Chem. Rev. 2009, 109, 3333
6. Kato, T., Maerten, E., and Baceiredo, A. Top. Organomet. Chem. 2010, 30, 131
7. Lavallo, V., Canac, Y., Donnadieu, B., Schoeller, W. W., and Bertrand, G. Science 2006, 312, 722
8. Schoeller, W. W., Frey, G. D., and Bertrand, G. Chem.-Eur. J. 2008, 14, 4711
9. N-Heterocyclic Carbenes in Transition Metal Catalysis; Glorius, F., Ed.; Topics in Organometallic Chemistry, Vol. 21; Springer: Berlin, 2007.
10. Martin, D., Baceiredo, A., Gornitzka, H., Schoeller, W. W., and Bertrand, G. Angew. Chem., Int. Ed. 2005, 44, 1700
11. Soleilhavoup, M., Baceiredo, A., Treutler, O., Ahlrichs, R., Nieger, M., and Bertrand, G. J. Am. Chem. Soc. 1992, 114, 10959
12. Treutler, O., Ahlrichs, R., and Soleilhavoup, M. J. Am. Chem. Soc. 1993, 115, 8788
13. Buron, C., Gornitzka, H., Romanenko, V., and Bertrand, G. Science 2000, 288, 834
14. Despagnet, E., Gornitzka, H., Rozhenko, A. B., Schoeller, W. W., Bourissou, D., and Bertrand, G. Angew. Chem., Int. Ed. 2002, 41, 2835
15. Despagnet-Ayoub, E., Gornitzka, H., Bourissou, D., and Bertrand, G. Eur. J. Org. Chem. 2003, 2039
16. Pelter, A., Singaram, B., and Wilson, J. W. Tetrahedron Lett. 1983, 24, 631
17. Cooke, M. P. J. Org. Chem. 1994, 59, 2930
18. Pelter, A. Pure Appl. Chem. 1994, 66, 223
19. Only a few boryldiazomethane derivatives have been described. See: Arthur, M. P., Baceiredo, A., and Bertrand, G. J. Am. Chem. Soc. 1991, 113, 5857
20. Weber, L., Wartig, H. B., Stammler, H.-G., and Neumann, B. Organometallics 2001, 20, 5248
21. Igau, A., Baceiredo, A., Grützmacher, H., Pritzkow, H., and Bertrand, G. J. Am. Chem. Soc. 1989, 111, 6853
22. Grützmacher, H. and Pritzkow, H. Angew. Chem., Int. Ed. 1991, 30, 709
23. Heim, U., Pritzkow, H., Schönberg, H., and Grützmacher, H. Chem. Commun. 1993, 673
24. Species 3 and 4 can be regarded as electron-deficient α-boryl carbocations. Calculations at the M05-2X/6-31G(d) level revealed that isomer 4 is 29.9 kcal/mol more stable than isomer 3, suggesting increased stabilization due to π donation from LP(N1) to LP(B) in 4.
25. Horchler von Locquenghien, K., Baceiredo, A., Boese, R., and Bertrand, G. J. Am. Chem. Soc. 1991, 113, 5062
26. Chiu, C.-W. and Gabbaï, F. P. Angew. Chem., Int. Ed. 2007, 46, 6878
27. Kato, T., Gornitzka, H., Baceiredo, A., Savin, A., and Bertrand, G. J. Am. Chem. Soc. 2000, 122, 998
28. Martin, D., Illa, O., Baceiredo, A., Bertrand, G., Ortuno, R. M., and Branchadell, V. J. Org. Chem. 2005, 70, 5671
29. Lecea, B., Ayerbe, M., Arrieta, A., Cossío, F. P., Branchadell, V., Ortuño, R. M., and Baceiredo, A. J. Org. Chem. 2007, 72, 357