Synthesis and reactivity of subvalent compounds Part 10. Fast deuterium labeling and the basicity of stable diamino carbenes (imidazole-2-ylidenes)

Journal of Organometallic Chemistry

Volumn 608, Issue 1-2, 2000, Pages 122-125

  Denk, Michael K ^a   Rodezno, José M ^a  

^a UNIVERSITY OF TORONTO   (Canada)

Author keywords

Carbenes; DFT calculations; Hydrogen deuterium exchange; Imidazol 2 ylidenes; Mechanism; Proton affinities

Indexed keywords

EID: 0001016617     PISSN: 0022328X     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0022-328X(00)00390-9     Document Type: Article

References (38)

1. (a) A. Igau, H. Grützmacher, A. Baceiredo, G. Bertrand, J. Am. Chem. Soc. 110 (1988) 6463.
2. (b) L. Nyulaszi, D. Szieberth, J. Reffy, T. Veszpremi, Theochem. J. Mol. Struct. 453 (1998) 91.
3. (c) D. Bourissou, O. Guerret, F.P. Gabbai, G. Bertrand, Chem. Rev. 100 (2000) 39.
4. (d) C. Buron, H. Gornitzka, V. Romanenko, G. Bertrand, Science 288 (2000) 834.
5. (a) A.J. Arduengo, R.L. Harlow, M. Kline, J. Am. Chem. Soc. 113 (1991) 361.
6. (b) A.J. Arduengo, H.V.R. Dias, R.L. Harlow, M. Kline, J. Am. Chem. Soc. 114 (1992), 5530.
7. (c) A.J. Arduengo, J. Goerlich, W. Marshall, J. Am. Chem. Soc. 117 (1995) 11027.
8. (d) A.J. Arduengo, F. Davidson, H.V.R. Dias, J.R. Goerlich, D. Khasnis, W.J. Marshall, T.K. Prakasha, J. Am. Chem. Soc. 119 (1997) 12 742.
9. R.W. Alder, M.E. Blake, C. Bortolotti, S. Bufali, C.P. Butts, E. Linehan, J.M. Oliva, A.G. Orpen, M.J. Quayle, J. Chem. Soc. Chem. Commun. (1999) 241.
10. (a) M.K. Denk, K. Hatano, M.J. Ma, Tetrahedron Lett. 40 (1999) 2057.
11. (b) J.F. Lehmann, S.G. Urquhart, L.E. Ennis, A. Hitchcock, K. Hatano, S. Gupta, M.K. Denk, Organometallics 18 (1999) 1862.
12. (c) M.K. Denk, A. Thadani, K. Hatano, A.J. Lough, Angew. Chem. Int. Ed. Engl. 36 (1997) 2607; Angew. Chem. 109 (1997) 2719.
13. (c) M.K. Denk, A. Thadani, K. Hatano, A.J. Lough, Angew. Chem. Int. Ed. Engl. 36 (1997) 2607; Angew. Chem. 109 (1997) 2719.
14. (a) M. Haaf, A. Schmiedl, T.A. Schmedake, R.A. Powell, A.J. Millevolte, M. Denk, R. West, J. Am. Chem. Soc. 120 (1998) 12714.
15. (b) S. Urquhart, A.P. Hitchcock, M.K. Denk, Organometallics 17 (1998) 2352.
16. (c) M.K. Denk, K. Hatano, A.J. Lough, Eur. J. Inorg. Chem. (1998) 1067.
17. (d) N. Metzler, M.K. Denk, J. Chem. Soc. Chem. Commun. (1996) 2657.
18. (e) R. West, M. Denk, Pure Appl. Chem. 68 (1996) 785.
19. (f) M. Denk, J.C. Green, N. Metzler, M. Wagner, J. Chem. Soc. Dalton Trans. (1994) 2405.
20. (g) M. Denk, R.K. Hayashi, R. West, J. Chem. Soc. Chem. Commun. (1994) 33.
21. (h) M. Denk, R. Lennon, R. Hayashi, R. West, A. Haaland, A.V. Belyakov, H.P. Verne, M. Wagner, N. Metzler, J. Am. Chem. Soc. 116 (1994) 2691.
22. (i) M. Denk, R.K. Hayashi, R. West, J. Am. Chem. Soc. 116 (1994) 10813.
23. (j) A.J. Arduengo, H. Bock, H. Chen, M. Denk, D.A. Dixon, J.C. Green, W.A. Herrmann, N.L. Jones, M. Wagner, R. West, J. Am. Chem. Soc. 116 (1994) 6641.
24. (a) W.A. Herrmann, M. Denk, J. Behm, W. Scherer, F.-R. Klingan, H. Bock, B. Solouki, M. Wagner, Angew. Chem. 104 (1992) 1489; Angew. Chem. Int. Ed. Engl. 31 (1992) 1485.
25. (a) W.A. Herrmann, M. Denk, J. Behm, W. Scherer, F.-R. Klingan, H. Bock, B. Solouki, M. Wagner, Angew. Chem. 104 (1992) 1489; Angew. Chem. Int. Ed. Engl. 31 (1992) 1485.
26. (b) M.K. Denk, M. Khan, A.J. Lough, K. Shuchi, Acta Crystallogr. Sect C 54 (1998) 1830.
27. (a) M.K. Denk, S. Gupta, R. Ramachandran, Eur. J. Inorg. Chem. (1999) 41.
28. (b) M.K. Denk, S. Gupta, R. Ramachandran, Tetrahedron Lett. (1996) 9025.
29. For a discussion of oxygen transfer reactions and their reaction energies see: R.H. Holm, J.P. Donahue, Polyhedron 12 (1993) 571 (Polyhedron Special Report 45).
30. R. Oda, M. Mieno, Y. Hayashi, Tetrahedron Lett. 25 (1967) 2363.
31. The protonation of stable carbenes at the carbene carbon atom has been previously investigated through calculations: (a) D.A. Dixon, A.J. Arduengo, J. Phys. Chem. 95 (1991) 4180. (b) R.W. Alder, M.E. Blake, J.M. Oliva, J. Phys. Chem. Sect. A 103 (1999) 11200.
32. The protonation of stable carbenes at the carbene carbon atom has been previously investigated through calculations: (a) D.A. Dixon, A.J. Arduengo, J. Phys. Chem. 95 (1991) 4180. (b) R.W. Alder, M.E. Blake, J.M. Oliva, J. Phys. Chem. Sect. A 103 (1999) 11200.
33. For the experimental generation of a diaminocarbene dication see: G.A. McGibbon, C. Heinemann, D.J. Lavorato, H. Schwarz, Angew. Chem. Int. Ed. Engl. 36 (1997) 1478.
34. The calculations were carried out with the SPARTAN-5.02 and GAUSSIAN-94 suite of programs: GAUSSIAN-94, Revision D.4, M.J. Frisch, G.W. Trucks, H.B. Schlegel, P.M.W. Gill, B.G. Johnson, M.A. Robb, J.R. Cheeseman, T. Keith, G.A. Petersson, J.A. Montgomery, K. Raghavachari, M.A. Al-Laham, V.G. Zakrzewski, J.V. Ortiz, J.B. Foresman, J. Cioslowski, B.B. Stefanov, A. Nanayakkara, M. Challacombe, C.Y. Peng, P.Y. Ayala, W. Chen, M.W. Wong, J.L. Andres, E.S. Replogle, R. Gomperts, R.L. Martin, D.J. Fox, J.S. Binkley, D.J. Defrees, J. Baker, J.P. Stewart, M. Head-Gordon, C. Gonzalez, and J.A. Pople, Gaussian, Inc., Pittsburgh PA, 1995. Molecular geometries were fully optimized and vibrational frequencies were calculated as indicated. The absence of virtual frequencies ensures that the calculated structures are minima rather than saddle points. Zero point vibrational energies: (b) J.B. Foresman, A. Frisch, Exploring Chemistry with Electronic Structure Methods, second ed., Gaussian Inc., Pittsburgh, PA, 1996. I. Bytheway, M.W. Wong, Chem. Phys. Lett. 282 (1998) 219. (d) A.P. Scott, L. Radom, J. Phys. Chem. 100 (1996) 16 502.
35. The calculations were carried out with the SPARTAN-5.02 and GAUSSIAN-94 suite of programs: GAUSSIAN-94, Revision D.4, M.J. Frisch, G.W. Trucks, H.B. Schlegel, P.M.W. Gill, B.G. Johnson, M.A. Robb, J.R. Cheeseman, T. Keith, G.A. Petersson, J.A. Montgomery, K. Raghavachari, M.A. Al-Laham, V.G. Zakrzewski, J.V. Ortiz, J.B. Foresman, J. Cioslowski, B.B. Stefanov, A. Nanayakkara, M. Challacombe, C.Y. Peng, P.Y. Ayala, W. Chen, M.W. Wong, J.L. Andres, E.S. Replogle, R. Gomperts, R.L. Martin, D.J. Fox, J.S. Binkley, D.J. Defrees, J. Baker, J.P. Stewart, M. Head-Gordon, C. Gonzalez, and J.A. Pople, Gaussian, Inc., Pittsburgh PA, 1995. Molecular geometries were fully optimized and vibrational frequencies were calculated as indicated. The absence of virtual frequencies ensures that the calculated structures are minima rather than saddle points. Zero point vibrational energies: (b) J.B. Foresman, A. Frisch, Exploring Chemistry with Electronic Structure Methods, second ed., Gaussian Inc., Pittsburgh, PA, 1996. I. Bytheway, M.W. Wong, Chem. Phys. Lett. 282 (1998) 219. (d) A.P. Scott, L. Radom, J. Phys. Chem. 100 (1996) 16 502.
36. The calculations were carried out with the SPARTAN-5.02 and GAUSSIAN-94 suite of programs: GAUSSIAN-94, Revision D.4, M.J. Frisch, G.W. Trucks, H.B. Schlegel, P.M.W. Gill, B.G. Johnson, M.A. Robb, J.R. Cheeseman, T. Keith, G.A. Petersson, J.A. Montgomery, K. Raghavachari, M.A. Al-Laham, V.G. Zakrzewski, J.V. Ortiz, J.B. Foresman, J. Cioslowski, B.B. Stefanov, A. Nanayakkara, M. Challacombe, C.Y. Peng, P.Y. Ayala, W. Chen, M.W. Wong, J.L. Andres, E.S. Replogle, R. Gomperts, R.L. Martin, D.J. Fox, J.S. Binkley, D.J. Defrees, J. Baker, J.P. Stewart, M. Head-Gordon, C. Gonzalez, and J.A. Pople, Gaussian, Inc., Pittsburgh PA, 1995. Molecular geometries were fully optimized and vibrational frequencies were calculated as indicated. The absence of virtual frequencies ensures that the calculated structures are minima rather than saddle points. Zero point vibrational energies: (b) J.B. Foresman, A. Frisch, Exploring Chemistry with Electronic Structure Methods, second ed., Gaussian Inc., Pittsburgh, PA, 1996. I. Bytheway, M.W. Wong, Chem. Phys. Lett. 282 (1998) 219. (d) A.P. Scott, L. Radom, J. Phys. Chem. 100 (1996) 16 502.
37. The calculations were carried out with the SPARTAN-5.02 and GAUSSIAN-94 suite of programs: GAUSSIAN-94, Revision D.4, M.J. Frisch, G.W. Trucks, H.B. Schlegel, P.M.W. Gill, B.G. Johnson, M.A. Robb, J.R. Cheeseman, T. Keith, G.A. Petersson, J.A. Montgomery, K. Raghavachari, M.A. Al-Laham, V.G. Zakrzewski, J.V. Ortiz, J.B. Foresman, J. Cioslowski, B.B. Stefanov, A. Nanayakkara, M. Challacombe, C.Y. Peng, P.Y. Ayala, W. Chen, M.W. Wong, J.L. Andres, E.S. Replogle, R. Gomperts, R.L. Martin, D.J. Fox, J.S. Binkley, D.J. Defrees, J. Baker, J.P. Stewart, M. Head-Gordon, C. Gonzalez, and J.A. Pople, Gaussian, Inc., Pittsburgh PA, 1995. Molecular geometries were fully optimized and vibrational frequencies were calculated as indicated. The absence of virtual frequencies ensures that the calculated structures are minima rather than saddle points. Zero point vibrational energies: (b) J.B. Foresman, A. Frisch, Exploring Chemistry with Electronic Structure Methods, second ed., Gaussian Inc., Pittsburgh, PA, 1996. I. Bytheway, M.W. Wong, Chem. Phys. Lett. 282 (1998) 219. A.P. Scott, L. Radom, J. Phys. Chem. 100 (1996) 16 502.
38. -3.