Insertion reactions of tantalum (V) carborane alkyl and aryl complexes with nitriles and isonitriles. Thermal and photochemical isomerization of η2-iminoacyl isomers1

Organometallics

Volumn 16, Issue 18, 1997, Pages 3993-4000

  Boring, Eric ^a   Sabat, Michal ^a   Finn, M G ^a   Grimes, Russell N ^a  

^a UNIVERSITY OF VIRGINIA   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0001558484     PISSN: 02767333     EISSN: None     Source Type: Journal    
DOI: 10.1021/om9703447     Document Type: Article

References (63)

1. Organotransition-Metal Metallacarboranes. 50. Part 49: Curtis, M. A.; Finn, M. G.; Grimes, R. N. J. Organomet. Chem., in press.
2. (a) Rodriguez, G.; Bazan, G. C. J. Am. Chem. Soc. 1997, 119, 343-352 and references therein.
3. (b) Crowther, D. J.; Baenziger, N. C.; Jordan, R. F. J. Am. Chem. Soc. 1991, 113, 1455-1457.
4. Lubben, T. V.; Wolczanski, P. T.; Van Duyne, G. D. Organometallics 1984, 3, 977-983.
5. Schafer, V.; Pritzkow, H.; Siebert, W. Angew. Chem., Int. Ed. Engl. 1988, 27, 299-300.
6. Kuhn, N.; Horn, E.-M; Zauder, E.; Blaser, D.; Boese, R. Angew. Chem., Int. Ed. Engl. 1988, 27, 579-580.
7. Stockman, K. E.; Houseknecht, K. L.; Boring, E. A.; Sabat, M.; Finn, M. G.; Grimes, R. N. Organometallics 1995, 14, 3014-3029.
8. Houseknecht, K. L.; Stockman, K. E.; Sabat, M.; Finn, M. G.; Grimes, R. N. J. Am. Chem. Soc. 1995, 117, 1163-1164.
9. 7
10. Broene, R. D.; Buchwald, S. L. Science 1993, 261, 1696-1701.
11. Buchwald, S. L.; Nielsen, R. B. Chem. Rev. 1988, 88, 1047-1058.
12. Alelyunas, Y. W.; Jordan, R. F.; Echols, S. F.; Borkowsky, S. L.; Bradley, P. K. Organometallics 1991, 10, 1406-1416 and references therein.
13. The niobium analogue of dimethyl complex 1 undergoes the same transformation with tert-butyl isocyanide, giving a 14:1 ratio of isomers, which is stable toward heating at 90 °C for several hours. The structure of the major isomer has not been determined conclusively, but the NMR trends match those observed for 5a vs 5b.
14. 2-iminoacyl complexes analogous to 5 and 6 and a thermal conversion analogous to the transformation of 5a to 5b.
15. Durfee, L. D.; Rothwell, I. P. Chem. Rev. 1988, 88, 1059-1079.
16. In contrast to the reaction of 7b, complex 6 (Scheme 3) is unchanged upon treatment with 2,6-dimethylphenyl isocyanide at room temperature.p However, when 6 is photolyzed in the presence of the isocyanide, four organometallic products are formed. These compounds were separated by preparative thin layer chromatography and shown by mass spectometry to have identical molecular weights corresponding to a 1:1 addition of the reaction components, but detailed structures cannot be proposed with the available data. It is likely that cage insertion chemistry similar to that shown in Scheme 4 also occurs in this case, since one of these isolated products displays a broadened singlet corresponding to a methyl group attached to boron. Similarly, complexes 5a and 5b do not react with excess t-BuNC at room temperature but do undergo reaction upon photolysis to give several products, which were also shown by mass spectrometry to incorporate one additional equivalent of isocyanide.
17. Grimes, R. N. Chem. Rev. 1992, 92, 251-268.
18. Siebert, W. Pure Appl. Chem. 1987, 59, 947-954.
19. Stockman, K. E.; Sabat, M.; Finn, M. G.; Grimes, R. N. J. Am. Chem. Soc. 1995, 117, 1163-1164.
20. Merkert, J. M.; Geiger, W. E.; Attwood, M. D.; Grimes, R. N. Organometallics 1991, 10, 3545.
21. Stephan, M.; Davis, J. H., Jr.; Meng, X.; Chase, K. P.; Hauss, J.; Zenneck, U.; Pritzkow, H.; Siebert, W.; Grimes, R. N. J. Am. Chem. Soc. 1992, 114, 5214-5221.
22. Doxsee, K. M.; Juliette, J. J. J.; Mouser, J. K. M.; Zientara, K. Organometallics 1993, 12, 4682-4686.
23. Doxsee, K. M.; Juliette, J. J. J.; Zientara, K.; Nieckarz, G. J. Am. Chem. Soc. 1994, 116, 2147-2148.
24. Horton, A. D.; Orpen, A. G. Organometallics 1991, 10, 3910-3918.
25. Leong, W. W.; Larock, R. C. In Comprehensive Organometallic Chemistry II; Hegedus, L. S., Ed.; Pergamon: Oxford, U.K. 1995; Vol. 12, Chapter 3.3, pp 131-160.
26. Bochmann, M. In Comprehensive Organometallic Chemistry II; Lappert, M. F., Ed.; Pergamon: Oxford, U.K. 1995; Vol. 4, Chapter 5, pp 273-431.
27. Soderberg, B. C. In Comprehensive Organometallic Chemistry II; Hegedus, L. S., Ed.; Pergamon: Oxford, U.K. 1995; Vol. 12, Chapter 3.5, pp 241-297.
28. Grigg, R.; Sridharan, V. In Comprehensive Organometallic Chemistry II; Hegedus, L. S., Ed.; Pergamon: Oxford, U.K. 1995; Vol. 12, Chapter 3.6, pp 299-321.
29. Jubb, J.; Song, J.; Richeson, D.; Gambarotta, S. In Comprehensive Organometallic Chemistry II; Lappert, M. F., Ed.; Pergamon: Oxford, U.K. 1995; Vol. 4, Chapter 11, pp 543-588.
30. Thebtavanonth, C.; Thebtavanonth, Y. In Cyclization Reactions; CRC Press: Ann Arbor, MI, 1994; pp 255-330.
31. Negishi, E.-I.; Takahashi, T. Acc. Chem. Res. 1994, 27, 124-130.
32. Michelin, R. A.; Mozzon, M.; Bertani, R. Coord. Chem. Rev. 1996, 147, 299-338.
33. Alelyunas, Y. W.; Guo, Z. Y.; Lapointe, R. E.; Jordan, R. F. Organometallics 1993, 12, 544-553.
34. Bochmann, M.; Wilson, L. M.; Hursthouse, M. B.; Motevalli, M. Organometallics 1988, 7, 1148-1154.
35. Doxsee, K. M.; Farahi, J. B. J. Chem. Soc., Chem. Commun. 1990, 1452-1454.
36. Hylakryspin, I.; Niu, S. Q.; Gleiter, R. Organometallics 1995, 14, 964-974.
37. For nitrile coupling reactions, see also: Doxsee, K. M.; Juliette, J. J. J.; Mouser, J. K. M.; Zientara, K. Organometallics 1993, 12, 4682-4686. Alvarado, Y.; Daff, P. J.; Perez, P. J.; Poveda, M. L.; Sanchezdelgado, R.; Carmona, E. Organometallics 1996, 15, 2192-2194. Temme, R.; Erker, G. J. organomet. Chem. 1995, 488, 177-182.
38. For nitrile coupling reactions, see also: Doxsee, K. M.; Juliette, J. J. J.; Mouser, J. K. M.; Zientara, K. Organometallics 1993, 12, 4682-4686. Alvarado, Y.; Daff, P. J.; Perez, P. J.; Poveda, M. L.; Sanchezdelgado, R.; Carmona, E. Organometallics 1996, 15, 2192-2194. Temme, R.; Erker, G. J. organomet. Chem. 1995, 488, 177-182.
39. For nitrile coupling reactions, see also: Doxsee, K. M.; Juliette, J. J. J.; Mouser, J. K. M.; Zientara, K. Organometallics 1993, 12, 4682-4686. Alvarado, Y.; Daff, P. J.; Perez, P. J.; Poveda, M. L.; Sanchezdelgado, R.; Carmona, E. Organometallics 1996, 15, 2192-2194. Temme, R.; Erker, G. J. organomet. Chem. 1995, 488, 177-182.
40. Erker, G.; Fromberg, W.; Atwood, J. L.; Hunter, W. E. Angew. Chem., Int. Ed. Engl. 1984, 23, 68-69.
41. Klei, E.; Teuben, J. H.; de Liefde Meijer, H. J. J. Chem. Soc., Chem. Commun. 1981, 342-344.
42. Fischer, H.; Markl, R.; Zeuner, S. J. Organomet. Chem. 1985, 286, 17-26.
43. Yang, D. C.; Dragisich, V.; Wulff, W. D.; Huffman, J. C. J. Am. Chem. Soc. 1988, 110, 307-309.
44. Knight, D. A.; Dewey, M. A.; Stark, G. A.; Bennett, B. K.; Arif, A. M.; Gladysz, J. A. Organometallics 1993, 12, 4523-4534.
45. Jacoby, D.; Isoz, S.; Floriani, C.; Schenk, K.; Chiesi-Villa, A.; Rizzoli, C. Organometallics 1995, 14, 4816-4824.
46. Ito, Y. Pure Appl. Chem. 1990, 62, 583-588.
47. Carofiglio, T.; Floriani, C.; Chiesi-Villa, A.; Guastini, C. Inorg Chem. 1989, 28, 4417-4419.
48. Guram, A. S.; Jordan, R. F. J. Org. Chem. 1993, 58, 5595-5597.
49. Honda, T.; Satoh, S.; Mori, M. Organometallics 1995, 14, 1548-1550.
50. Curtis, M. D.; Real, J.; Hirpo, W.; Butler, W. M. Organometallics 1990, 9, 66-74.
51. 2-iminoacyl isomers.
52. 2-iminoacyl system is provided. See: Antiñolo, A.; Fajardo, M.; Gil-Sanz, R.; López-Mardomingo, C.; Martin-Villa, P.; Otero, A.; Kubicki, M. M.; Mugnier, Y.; El Krami, S.; Mourad, Y. Organometallics 1993, 12, 381-388.
53. Erker, G. Acc. Chem. Res. 1984, 17, 103-109.
54. However, 5a cannot definitively be assigned as the "kinetic" product since the same 4:1 ratio of isomers is obtained when the reaction is conducted at -78 °C.
55. 2-iminoacyl ligand to give metallacycle intermediates. See: Filippou, A. C.; Volkl, C.; Kiprof, P. J. Organomet. Chem. 1991, 415, 375-394.
56. M-C = 0.074 Å. Isoz, S.; Floriani, C.; Schenk, K.; Chiesi-Villa, A.; Rizzoli, C. Organometallics 1996, 15, 337-344.
57. M-c = 0.010 Å. Jacoby, D.; Isoz, S.; Floriani, C.; Schenk, K.; Chiesi-Villa, A.; Rizzoli, C. Organometallics 1995, 14, 4816-4824.
58. M-c = 0.065 Å. Fandos, R.; Lanfranchi, M.; Otero, A.; Pellinghelli, M. A.; Ruiz. M. J.; Terreros, P. Organometallics 1996, 15, 4725-4730.
59. M-C = 0.015, 0.023 Å. Berg, F. J.; Petersen, J. L. Organometallics 1993, 12, 3890-3895.
60. M-C = 0.005 Å. Pizzano, A.; Sánchez, L.; Altmann, M.; Monge, A.; Ruiz, C.; Carmona, E. J. Am. Chem. Soc. 1995, 117, 1759-1765.
61. M-C = -0.038, -0.001 Å. Laï, R.; Desbois, O.; Zamkotsian, F.; Faure, R.; Feneau-Dupont, J.; Declercq, J.-P. Organometallics 1995, 14, 2145-2147.
62. TEXSAN 5.0: Single Crystal Structure Analysis Software; Molecular Structure Corp.: The Woodlands, TX, 1989.
63. Burla, M. C.; Camalli, M.; Gascarano, G.; Giacovazzo, C.; Polidori, G.; Spagna, R.; Viterbo, D. J. Appl. Crystallogr. 1989, 22, 389