On the electronic structure of (phosphino)(silyl)carbenes: Single- crystal X-ray diffraction and ELF analyses [25]

Journal of the American Chemical Society

Volumn 122, Issue 5, 2000, Pages 998-999

  Kato, Tsuyoshi ^a   Gornitzka, Heinz ^a   Baceiredo, Antoine ^a   Savin, Andreas ^b   Bertrand, Guy ^a  

^a Appliquee UMR CNRS 5069 Equipe Ligands Bifonctionnels et Polymeres Biodegradables   (France)

^b LABORATOIRE DE CHIMIE THÉORIQUE   (France)

Author keywords

[No Author keywords available]

Indexed keywords

CARBENE;

CHEMICAL REACTION; CHEMICAL STRUCTURE; LETTER; REACTION ANALYSIS; STRUCTURE ANALYSIS; X RAY DIFFRACTION;

EID: 0034624444     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja9939542     Document Type: Letter

References (34)

1. For reviews on stable singlet carbenes, see: (a) Bourissou, D.; Guerret, O.; Gabbai, F.; Bertrand, G. Chem. Rev. 2000, 100, 39-92. (b) Herrmann, W. A.; Köcher, C. Angew. Chem., Int. Ed. Engl. 1997, 36, 2163-2187. (c) Arduengo, A. J., III; Krafczyk, R. Chem. Unserer Zeit 1998, 32, 6-14.
2. For reviews on stable singlet carbenes, see: (a) Bourissou, D.; Guerret, O.; Gabbai, F.; Bertrand, G. Chem. Rev. 2000, 100, 39-92. (b) Herrmann, W. A.; Köcher, C. Angew. Chem., Int. Ed. Engl. 1997, 36, 2163-2187. (c) Arduengo, A. J., III; Krafczyk, R. Chem. Unserer Zeit 1998, 32, 6-14.
3. For reviews on stable singlet carbenes, see: (a) Bourissou, D.; Guerret, O.; Gabbai, F.; Bertrand, G. Chem. Rev. 2000, 100, 39-92. (b) Herrmann, W. A.; Köcher, C. Angew. Chem., Int. Ed. Engl. 1997, 36, 2163-2187. (c) Arduengo, A. J., III; Krafczyk, R. Chem. Unserer Zeit 1998, 32, 6-14.
4. For calculations on aminocarbenes, see: (a) Heinemann, C.; Thiel, W. Chem. Phys. Lett. 1994, 217, 11-16. (b) Heinemann, C.; Müller, T.; Apeloig, Y.; Schwarz, H. J. Am. Chem. Soc. 1996, 118, 2023-2038. (c) Boehme, C.; Frenking, G. J. Am. Chem. Soc. 1996, 118, 2039-2046. (d) Sauers, R. R. Tetrahedron Lett. 1996, 37, 149-152. (e) Raabe, G.; Breuer, K.; Enders, D.; Teles, J. H. Z. Naturforsch. 1996, 51a, 95-101.
5. For calculations on aminocarbenes, see: (a) Heinemann, C.; Thiel, W. Chem. Phys. Lett. 1994, 217, 11-16. (b) Heinemann, C.; Müller, T.; Apeloig, Y.; Schwarz, H. J. Am. Chem. Soc. 1996, 118, 2023-2038. (c) Boehme, C.; Frenking, G. J. Am. Chem. Soc. 1996, 118, 2039-2046. (d) Sauers, R. R. Tetrahedron Lett. 1996, 37, 149-152. (e) Raabe, G.; Breuer, K.; Enders, D.; Teles, J. H. Z. Naturforsch. 1996, 51a, 95-101.
6. For calculations on aminocarbenes, see: (a) Heinemann, C.; Thiel, W. Chem. Phys. Lett. 1994, 217, 11-16. (b) Heinemann, C.; Müller, T.; Apeloig, Y.; Schwarz, H. J. Am. Chem. Soc. 1996, 118, 2023-2038. (c) Boehme, C.; Frenking, G. J. Am. Chem. Soc. 1996, 118, 2039-2046. (d) Sauers, R. R. Tetrahedron Lett. 1996, 37, 149-152. (e) Raabe, G.; Breuer, K.; Enders, D.; Teles, J. H. Z. Naturforsch. 1996, 51a, 95-101.
7. For calculations on aminocarbenes, see: (a) Heinemann, C.; Thiel, W. Chem. Phys. Lett. 1994, 217, 11-16. (b) Heinemann, C.; Müller, T.; Apeloig, Y.; Schwarz, H. J. Am. Chem. Soc. 1996, 118, 2023-2038. (c) Boehme, C.; Frenking, G. J. Am. Chem. Soc. 1996, 118, 2039-2046. (d) Sauers, R. R. Tetrahedron Lett. 1996, 37, 149-152. (e) Raabe, G.; Breuer, K.; Enders, D.; Teles, J. H. Z. Naturforsch. 1996, 51a, 95-101.
8. For calculations on aminocarbenes, see: (a) Heinemann, C.; Thiel, W. Chem. Phys. Lett. 1994, 217, 11-16. (b) Heinemann, C.; Müller, T.; Apeloig, Y.; Schwarz, H. J. Am. Chem. Soc. 1996, 118, 2023-2038. (c) Boehme, C.; Frenking, G. J. Am. Chem. Soc. 1996, 118, 2039-2046. (d) Sauers, R. R. Tetrahedron Lett. 1996, 37, 149-152. (e) Raabe, G.; Breuer, K.; Enders, D.; Teles, J. H. Z. Naturforsch. 1996, 51a, 95-101.
9. For calculations on phosphinocarbenes, see: (a) Nguyen, M. T.; McGinn, M. A.; Hegarty, A. F. Inorg. Chem. 1986, 25, 2185-2190. (b) Dixon, D. A.; Dobbs, K. B.; Arduengo, A. J., III; Bertrand, G. J. Am. Chem. Soc. 1991, 113, 8782-8785. (c) Treutler, O.; Ahlrichs, R.; Soleilhavoup, M. J. Am. Chem. Soc. 1993, 115, 8788-8792. (d) Nyulaszi, L.; Szieberth, D.; Reffy, J.; Veszpremi, T. THEOCHEM 1998, 453, 91-95.
10. For calculations on phosphinocarbenes, see: (a) Nguyen, M. T.; McGinn, M. A.; Hegarty, A. F. Inorg. Chem. 1986, 25, 2185-2190. (b) Dixon, D. A.; Dobbs, K. B.; Arduengo, A. J., III; Bertrand, G. J. Am. Chem. Soc. 1991, 113, 8782-8785. (c) Treutler, O.; Ahlrichs, R.; Soleilhavoup, M. J. Am. Chem. Soc. 1993, 115, 8788-8792. (d) Nyulaszi, L.; Szieberth, D.; Reffy, J.; Veszpremi, T. THEOCHEM 1998, 453, 91-95.
11. For calculations on phosphinocarbenes, see: (a) Nguyen, M. T.; McGinn, M. A.; Hegarty, A. F. Inorg. Chem. 1986, 25, 2185-2190. (b) Dixon, D. A.; Dobbs, K. B.; Arduengo, A. J., III; Bertrand, G. J. Am. Chem. Soc. 1991, 113, 8782-8785. (c) Treutler, O.; Ahlrichs, R.; Soleilhavoup, M. J. Am. Chem. Soc. 1993, 115, 8788-8792. (d) Nyulaszi, L.; Szieberth, D.; Reffy, J.; Veszpremi, T. THEOCHEM 1998, 453, 91-95.
12. For calculations on phosphinocarbenes, see: (a) Nguyen, M. T.; McGinn, M. A.; Hegarty, A. F. Inorg. Chem. 1986, 25, 2185-2190. (b) Dixon, D. A.; Dobbs, K. B.; Arduengo, A. J., III; Bertrand, G. J. Am. Chem. Soc. 1991, 113, 8782-8785. (c) Treutler, O.; Ahlrichs, R.; Soleilhavoup, M. J. Am. Chem. Soc. 1993, 115, 8788-8792. (d) Nyulaszi, L.; Szieberth, D.; Reffy, J.; Veszpremi, T. THEOCHEM 1998, 453, 91-95.
13. (a) Karsch, H. H.; Zellner, K.; Mikulcik, P.; Lachmann, J.; Müller, G. Organometallics 1990, 9, 190-194.
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16. (b) Igau, A.; Baceiredo, A.; Trinquier, G.; Bertrand, G. Angew. Chem., Int. Ed. Engl. 1989, 28, 621-622.
17. 3d found that the bent structure (P-C-Si angle: 138.2°) was 0.83 kcal/mol lower in energy than the linear structure.
18. P-C = 152.9 Hz, P-C).
19. (a) Neemann, J.; Klingebiel, U. Chem. Ber. 1981, 114, 527-535.
20. (b) Scherer, O. J.; Püttmann, M.; Krüger, C.; Wolmershäuser, G. Chem. Ber. 1982, 115, 2076-2124.
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22. 3, Z = 2, T = 173(2) K.; R1 [for F > 2σ(F)] = 0.035 and wR2 = 0.083.
23. Regitz, M.; Scherer, O. J. Multiple Bonds and Low Coordination in Phosphorus Chemistry; Thieme: Stuttgart, 1990.
24. 8c
25. (a) Becke, A. D.; Edgecombe, K. E. J. Chem. Phys. 1990, 92, 5397-5403.
26. (b) Silvi, B.; Savin, A. Nature 1994, 371, 683-686.
27. (c) Savin, A.; Becke, A. D.; Flad, J.; Nesper, R.; Preuss, H.; von Schering, H. G. Angew. Chem., Int. Ed. Engl. 1991, 30, 409-412.
28. (d) Savin, A.; Nesper, R.; Wengert, S.; Fässler, T. H. Angew. Chem., Int. Ed. Engl. 1997, 36, 1809-1832.
29. +G(2d) basis sets. The linear form 2′ was characterized as an energy minimum by vibrational analysis. The ELF calculations were performed with the TopMod program written by Noury, S.; Krokidis, X.; Fuster, F.; Silvi, B. Laboratoire de Chimie Théorique, CNRS and Université Paris VI: Paris, France, 1997.
30. +G(2d) basis sets. The linear form 2′ was characterized as an energy minimum by vibrational analysis. The ELF calculations were performed with the TopMod program written by Noury, S.; Krokidis, X.; Fuster, F.; Silvi, B. Laboratoire de Chimie Théorique, CNRS and Université Paris VI: Paris, France, 1997.
31. (a) Cowley, A. H.; Gabbai, F. P.; Carrano, C. J.; Mokry, L. M.; Bond, M. R.; Bertrand, G. Angew. Chem., Int. Ed. Engl. 1994, 33, 578-580.
32. (b) Goumri, S.; Polischuck, O.; Gomitzka, H.; Baceiredo, A.; Bertrand, G. Angew. Chem., Int. Ed. 1999, 38, 3727-3729.
33. See also the ELF plot for HCCH in Figure 2 of ref 13d.
34. Goumri, S.; Leriche, Y.; Gornitzka, H.; Baceiredo, A.; Bertrand, G. Eur. J. Inorg. Chem. 1998, 1, 1539-1542 and references therein.