Ruthenated acetonitrile: Unusual brønsted acidity of a polar "Aprotic" solvent

Organometallics

Volumn 27, Issue 19, 2008, Pages 5025-5032

  Derrah, Eric J ^a   Giesbrecht, Karina E ^a   McDonald, Robert ^b   Rosenberg, Lisa ^a  

^a UNIVERSITY OF VICTORIA   (Canada)

^b UNIVERSITY OF ALBERTA   (Canada)

Author keywords

[No Author keywords available]

Indexed keywords

ACETONE; ACETONITRILE; ACIDS; ACTIVATION ANALYSIS; DYES; NUCLEAR MAGNETIC RESONANCE; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; PYRIDINE; SOLVENTS;

ALTERNATE ROUTES; APROTIC; BENZONITRILE; C-H ACTIVATIONS; DONOR SOLVENTS; DOUBLE BONDS; HIGHER TEMPERATURES; INDENYL; ISOTOPOMERS; METALATED COMPLEXES; METALATION; MULTIPLE PRODUCTS; NMR STUDIES; PHOSPHIDE LIGANDS;

ORGANIC SOLVENTS;

EID: 54249152703     PISSN: 02767333     EISSN: None     Source Type: Journal    
DOI: 10.1021/om800343x     Document Type: Article

References (52)

1. Collman, J. P.; Hegedus, L. S.; Norton, J. R.; Finke, R. G. Principles and Applications of Organe-transition Metal Chemistry; University Science Books: Sausalito, CA, 1987; p 199.
2. Storhoff, B. N.; Lewis, H. C. Coord. Chem. Rev. 1977, 23, 1.
3. See for example:Pittard, K. A.; Cundari, T. R.; Gunnoe, T. B.; Day, C. S.; Petersen, J. L. Organometallics 2005, 24, 5015.
4. Bianchini, C.; Meli, A.; Moneti, S.; Vizza, F. Organometallics 1998, 17, 2636.
5. Joshi, A. M.; MacFarlane, K. S.; James, B. R.; Frediana, P. Chem. Ind. (Dekker) 1994, 53, 497.
6. Chin, C. S.; Lee, B. Catalysis 1992, 14, 135.
7. Rhodes, L. F.; Venanzi, L. M. Inorg. Chem. 1987, 26, 2692.
8. Grey, R. A.; Pez, G. P.; Wallo, A. J. Am. Chem. Soc. 1981, 103, 7536.
9. Atesin, T. A.; Li, T.; Lachaize, S.; Brennessel, W. W.; Garcia, J. J.; Jones, W. D. J. Am. Chem. Soc. 2007, 129, 7562.
10. 2O.
11. The C-H bond strength in acetonitrile is ∼97 kcal/mol. Lide, D. R., Ed. CRC Handbook of Chemistry and Physics; CRC Press: Boca Raton, FL, 1987; pp 9-61.
12. 3CN: Fujita, E.; Creutz, C. Inorg. Chem. 1994, 33, 1729.
13. (b) Formation of novel crotonitrileamido ligands from acetonitrile metalation at yttrium: Duchateau, R.; vanWee, C. T.; Teuben, J. H. Organometallics 1996, 15, 2291.
14. (c) α-C-H activation of nitriles: Murahashi, S.; Takaya, H. Acc. Chem. Res. 2000, 33, 225.
15. English, A. D.; Herskovitz, T. J. Am. Chem. Soc. 1977, 99, 1648.
16. Ittel, S. D.; Tolman, C. A.; English, A. D.; Jesson, J. P. J. Am. Chem. Soc. 1978, 100, 7577.
17. Heeres, H. J.; Meetsma, A.; Teuben, J. H. Angew. Chem., Int. Ed. Engl. 1990, 29, 420.
18. (a) Ros, R.; Bataillard, R.; Roulet, R. J. Organomet. Chem. 1976, 118, C53.
19. (b) Ros, R.; Renaud, J.; Roulet, R. Helv. Chim. Acta 1975, 58, 133.
20. Davidson, J. G.; Barefield, E. K.; Vanderveer, D. G. Organometallics 1985, 4, 1178.
21. Derrah, E. J.; Pantazis, D. A.; McDonald, R.; Rosenberg, L. Organometallics 2007, 26, 1473.
22. Derrah, E. J.; Pantazis, D. A.; McDonald, R.; Hall, S. A.; Rosenberg, L., manuscript in preparation.
23. -1: SDBSWeb: http://riodb01.ibase.aist.go.jp/sdbs/ (National Institute of Advanced Industrial Science and Technology, July 25, 2007).
24. -1. Juchnovski, I. N.; Dimitrova, J. S.; Binev, I. G.; Kaneti, J. Tetrahedron 1978, 34, 779.
25. 2CN complexes.
26. 2;
27. Wood, C. D.; McLain, S. J.; Schrock, R. R. J. Am. Chem. Soc. 1979, 101, 3210), we see no evidence for this reaction.
28. 3).
29. (a) This switch in phosphide coordination mode (planar vs pyramidal) is similar to the well-established hemilability of the nitrosyl ligand (linear vs bent), as has been noted previously: Bohle, D. S.; Jones, T. C.; Rickard, C. E. F.; Roper, W. R. Organometallics 1986, 5, 1612. Similar adduct formation is observed for other "operationally unsaturated", five-coordinate ruthenium complexes:
30. (b) Johnson, T. J.; Foiling, K.; Streib, W. E.; Martin, J. D.; Huffman, J. C.; Jackson, S. A.; Eisenstein, O.; Caulton, K. G. Inorg. Chem. 1995, 34, 488.
31. (a) Planas, J. G.; Hampel, F.; Gladysz, J. A. Chem.-Eur. J. 2005, 11, 1402.
32. 3-acetonitrile. (See Experimental Section.)
33. 2)] (ref 13), the absence of this product in samples of 1 and excess benzonitrile that have stood for 24 h or longer suggests that reversible formation of 6 is fast relative to the orthometalation reaction (i.e., lifetimes of 1 in the equilibrium mixtures are sufficiently short to preclude this slow thermal decomposition)
34. (b) We see no evidence for the analogous, reversible dissociation of CO from complex 5 in solution. (See Experimental Section.)
35. A useful measure of "donicity" (Lewis basicity) of the solvents studied is their donor number, "DN". (a) Gutmann, V.; Schmid, R. Coord. Chem. Rev. 1974, 12, 263.
36. (b) For pyridine, acetonitrile, and benzonitrile, DN = 33.1, 14.1, and 11.9, respectively.
37. a(kcal/mol) = 9.3, 7.2. See Supporting Information for full details.
38. 6 in the NMR sample render this experiment a bit messy and difficult to monitor to completion.
39. 3-acetonitrile.
40. See Chan, V. S.; Stewart, I. C.; Bergman, R. G.; Toste, F. D. J. Am. Chem. Soc. 2006, 128, 2786
41. and Scriban, C.; Glueck, D. S. J. Am. Chem. Soc. 2006, 128, 2788 and references therein.
42. Pantazis, D. A., personal communication.
43. 3).
44. 2O) > 19.0 (MeOH) > 18.0 (water, although this is much higher, 33, for bulk water) > 17 (acetone). In ref 23, the authors note that, although overall trends in DN for any given heteroatom donor type are valid, comparisons between different heteroatom donors are not reliable.
45. 2], with loss of naphthalene (ref 9);
46. 2O: Bryndza, H. E.; Fong, L. K.; Paciello, R. A.; Tam, W.; Bercaw, J. E. J. Am. Chem. Soc. 1987, 109, 1444.
47. Derrah, E. J.; Marlinga, J. C.; Mitra, D.; Friesen, D. M.; Hall, S. A.; McDonald, R.; Rosenberg, L. Organometallics 2005, 24, 5817.
48. For these reactions, amounts of unreacted 1a,b include 12% or 16% that exist as the phosphaalkene structural isomers (see ref 13).
49. 1H NMR spectra of purified benzonitrile: 1a,b is apparently scavenging the trace amounts of α-aminotoluene present in the excess benzonitrile added.
50. Programs for diffractometer operation, data collection, data reduction, and absorption correction were those supplied by Bruker.
51. Beurskens, P. T.; Beurskens, G.; de.Gelder, R.; Garcia.Granda, S.; Israel, R.; Gould, R. O.; Smits, J. M. M. The DIRDIF-99 Program System; Crystallography Laboratory, University of Nijmegen: The Netherlands, 1999.
52. Sheldrick, G. M. Acta Crystallogr. 2008, A64, 112-122.