Selective activation of the ortho C?F bond in pentafluoropyridine by zerovalent nickel: Reaction via a metallophosphorane intermediate stabilized by neighboring group assistance from the pyridyl nitrogen

Organometallics

Volumn 29, Issue 7, 2010, Pages 1824-1831

  Nova, Ainara ^a   Reinhold, Meike ^a   Perutz, Robin N ^a   MacGregor, Stuart A ^b   McGrady, John E ^c  

^a UNIVERSITY OF YORK   (United Kingdom)

^b HERIOT WATT UNIVERSITY   (United Kingdom)

^c UNIVERSITY OF OXFORD   (United Kingdom)

Author keywords

[No Author keywords available]

Indexed keywords

BENZYNE; BOND ACTIVATION; CHEMO-SELECTIVITY; COORDINATION MODES; METAL CENTERS; METALLOPHOSPHORANE; NICKEL COMPLEX; OXIDATIVE ADDITIONS; PENTAFLUOROPYRIDINE; PHOSPHINE LIGANDS; PYRIDYL; REACTION PATHWAYS; SELECTIVE ACTIVATION; TRANSITION STATE; ZEROVALENT;

CHEMICAL BONDS; DENSITY FUNCTIONAL THEORY; FLUORINE; HYDROCARBONS; LIGANDS; NICKEL ALLOYS; NITROGEN; PHOSPHORUS COMPOUNDS; PLATINUM; QUANTUM CHEMISTRY; REACTION INTERMEDIATES;

BIOACTIVITY;

EID: 77950841417     PISSN: 02767333     EISSN: 15206041     Source Type: Journal    
DOI: 10.1021/om100064z     Document Type: Article

References (95)

1. Müller, K.; Faeh, C.; Diederich, F. Science 2007, 317, 1881
2. Purser, S.; Moore, P. R.; Swallow, S.; Gouverneur, V. Chem. Soc. Rev. 2008, 37, 320
3. Smart, B. E. J. Fluorine Chem. 2001, 109, 3
4. Amii, H.; Uneyama, K. Chem. Rev. 2009, 109, 2119
5. Braun, T.; Perutz, R. N. Transition-Metal Mediated C?F Bond Activation. In Comprehensive Organometallic Chemistry III; Crabtree, R. H.,; Mingos, D. M. P., Eds.; Elsevier: Amsterdam, 2006; Vol. 1, Chapter 26.
6. Torrens, H. Coord. Chem. Rev. 2005, 249, 1957
7. Perutz, R. N.; Braun, T. Chem. Commun. 2002, 2749
8. Jones, W. D. Dalton Trans. 2003, 3991
9. Burdeniuc, J.; Jedlicka, B.; Crabtree, R. H. Chem. Ber. 1997, 130, 145
10. Murphy, E. F.; Murugavel, R.; Roesky, H. W. Chem. Rev. 1997, 97, 3425
11. Kiplinger, J. L.; Richmond, T. G.; Osterberg, C. E. Chem. Rev. 1994, 94, 373
12. Braun, T.; Perutz, R. N.; Sladek, M. I. Chem. Commun. 2001, 2254
13. Steffen, A.; Sladek, M. I.; Braun, T.; Neumann, B.; Stammler, H. G. Organometallics 2005, 24, 4057
14. Kiso, Y.; Tamao, K.; Kumada, M. J. Organomet. Chem. 1973, 50, C12
15. Böhm, V. P. W.; Gstöttmayr, C. W. K.; Weskamp, T.; Herrmann, W. A. Angew. Chem., Int. Ed. 2001, 40, 3387
16. Dankwardt, J. W. J. Organomet. Chem. 2005, 690, 932
17. Ackermann, L.; Born, R.; Spatz, J. H.; Meyer, D. Angew. Chem., Int. Ed. 2005, 44, 7216
18. Lamm, K.; Stollenz, M.; Meier, M.; Gorls, H.; Walther, D. J. Organomet. Chem. 2003, 681, 24
19. Mongin, F.; Mojovic, L.; Guillamet, B.; Trecourt, F.; Queguiner, G. J. Org. Chem. 2002, 67, 8991
20. Widdowson, D. A.; Wilhelm, R. Chem. Commun. 2003, 578
21. Widdowson, D. A.; Wilhelm, R. E. Chem. Commun. 1999, 2211
22. Wilhelm, R.; Widdowson, D. A. J. Chem. Soc., Perkin Trans. 1 2000, 3808
23. Schaub, T.; Backes, M.; Radius, U. J. Am. Chem. Soc. 2006, 128, 15964
24. Aizenberg, M.; Milstein, D. Science 1994, 265, 359
25. Aizenberg, M.; Milstein, D. J. Am. Chem. Soc. 1995, 117, 8674
26. Vela, J.; Smith, J. M.; Yu, Y.; Ketterer, N. A.; Flaschenriem, C. J.; Lachicotte, R. J.; Holland, P. L. J. Am. Chem. Soc. 2005, 127, 7857
27. Meier, G.; Braun, T. Angew. Chem., Int. Ed. 2009, 48, 1546
28. Braun, T.; Noveski, D.; Ahijado, M.; Wehmeier, F. Dalton Trans. 2007, 3820
29. Reade, S. P.; Mahon, M. F.; Whittlesey, M. K. J. Am. Chem. Soc. 2009, 131, 1861
30. Fuchibe, K.; Ohshima, Y.; Mitomi, K.; Akiyama, T. J. Fluorine Chem. 2007, 128, 1158
31. Scott, V. J.; Çelenligil-Çetin, R.; Ozerov, O. V. J. Am. Chem. Soc. 2005, 127, 2852
32. Douvris, C.; Ozerov, O. V. Science 2008, 321, 1188
33. Johnson, S. A.; Huff, C. W.; Mustafa, F.; Saliba, M. J. Am. Chem. Soc. 2008, 130, 17278
34. Johnson, S. A.; Taylor, E T.; Cruise, S. J. Organometallics 2009, 28, 3842
35. 2] with tetrafluorobenzene, but these give way to the thermodynamic C?F activation products. (9)
36. Cronin, L.; Higgitt, C. L.; Karch, R.; Perutz, R. N. Organometallics 1997, 16, 4920
37. Archibald, S. J.; Braun, T.; Gaunt, J. F.; Hobson, J. E.; Perutz, R. N. J. Chem. Soc., Dalton Trans. 2000, 2013
38. Braun, T.; Cronin, L.; Higgitt, C. L.; McGrady, J. E.; Perutz, R. N.; Reinhold, M. New J. Chem. 2001, 25, 19
39. Burling, S.; Elliott, P. I. P.; Jasim, N. A.; Lindup, R. J.; McKenna, J.; Perutz, R. N.; Archibald, S. J.; Whitwood, A. C. Dalton Trans. 2005, 3686
40. Schaub, T.; Fischer, P.; Steffen, A.; Braun, T.; Radius, U.; Mix., A. J. Am. Chem. Soc. 2008, 130, 9304
41. Schaub, T.; Radius, U. Chem. Eur. J. 2005, 11, 5024
42. Doster, M. E.; Johnson, S. A. Angew. Chem., Int. Ed. 2009, 48, 2185
43. Reinhold, M.; McGrady, J. E.; Perutz, R. N. J. Am. Chem. Soc. 2004, 126, 5268
44. Campeau, L.-C.; Fagnou, K. Chem. Commun. 2006, 1253
45. Lafrance, M.; Rowley, C. N.; Woo, T. K.; Fagnou, K. J. Am. Chem. Soc. 2006, 128, 8754
46. Lafrance, M.; Shore, D.; Fagnou, K. Org. Lett. 2006, 8, 5097
47. Bedford, R. B.; Betham, M.; Charmant, J. P. H.; Weeks, A. L. Tetrahedron 2008, 64, 6038.
48. Oi, S.; Funayama, R.; Hattori, T.; Inoue, Y. Tetrahedron 2008, 64, 6051
49. Do, H.-Q.; Daugulis, O. J. Am. Chem. Soc. 2008, 130, 1128
50. Nakao, Y.; Kashihara, N.; Kanyiva, K. S.; Hiyama, T. J. Am. Chem. Soc. 2008, 130, 16170
51. Holtcamp, M. W.; Labinger, J. A.; Bercaw, J. E. J. Am. Chem. Soc. 1997, 119, 848
52. Holtcamp, M. W.; Henling, L. N.; Day, M. W.; Labinger, J. A.; Bercaw, J. E. Inorg. Chim. Acta 1998, 270, 467
53. Huhmann-Vincent, J.; Scott, B. L.; Kubas, G. J. Inorg. Chem. 1999, 38, 115
54. Basus, S.; Arulsamy, S.; Roddick, D. M. Organometallics 2008, 27, 3659
55. Perutz, R. N.; Rendon, N. Unpublished
56. Veits, Y. A.; Karlstedt, N. B.; Chuchuryukin, A. V.; Beletskaya, I. P. Russ. J. Org. Chem. 2000, 36, 750
57. Jasim, N. A.; Perutz, R. N.; Whitwood, A. C.; Braun, T.; Izundu, J.; Neumann, B.; Rothfeld, S.; Stammler, H. G. Organometallics 2004, 23, 6140
58. Jäger-Fiedler, U.; Arndt, P.; Baumann, W.; Spannenberg, A.; Burlakov, V. V.; Rosenthal, U. Eur. J. Inorg. Chem. 2005, 2842
59. Piglosiewicz, I. M.; Kraft, S.; Beckhaus, R.; Haase, D.; Saak, W. Eur. J. Inorg. Chem. 2005, 938
60. Braun, T.; Cronin, L.; Higgitt, C. L.; McGrady, J. E.; Perutz, R. N.; Reinhold, M. New J. Chem. 2001, 25, 19
61. Macgregor, S. A.; Roe, D. C.; Marshall, W. J.; Bloch, K. M.; Bakhmutov, V. I.; Grushin, V. V. J. Am. Chem. Soc. 2005, 127, 15304
62. Macgregor, S. A. Chem. Soc. Rev. 2007, 35, 67
63. Macgregor, S. A.; Wondimagegn, T. Organometallics 2007, 26, 1143
64. Erhardt, S.; Macgregor, S. A. J. Am. Chem. Soc. 2008, 130, 15490
65. Nova, A.; Erhardt, S.; Jasim, N. A.; Perutz, R. N.; Macgregor, S. A.; McGrady, J. E.; Whitwood, A. C. J. Am. Chem. Soc. 2008, 130, 15499
66. Hofmann, P.; Unfried, G. Chem. Ber. 1992, 125, 659
67. Bosque, R.; Clot, E.; Fantacci, S.; Maseras, F.; Eisenstein, O.; Perutz, R. N.; Renkema, K. B.; Caulton, K. G. J. Am. Chem. Soc. 1998, 120, 12634
68. Maron, L.; Werkema, E. L.; Perrin, L.; Eisenstein, O.; Andersen, R. A. J. Am. Chem. Soc. 2005, 127, 279
69. Clot, E.; Mégret, C.; Eisenstein, O.; Perutz, R. N. J. Am. Chem. Soc. 2009, 131, 7817.
70. Frisch, M. J. Gaussian 03, Revision B.03; Pittsburgh, PA, 2003.
71. Becke, A. D. Phys. Rev. A 1988, 38, 3098
72. Becke, A. D. J. Chem. Phys. 1993, 98, 1372
73. Becke, A. D. J. Chem. Phys. 1993, 98, 5648
74. Vosko, S. H.; Wilk, L.; Nusair, M. Can. J. Phys. 1980, 58, 1200
75. Lee, C.; Yang, W.; Parr, R. G. Phys. Rev. B 1988, 37, 785
76. Becke, A. D. J. Chem. Phys. 1986, 84, 4524
77. Perdew, J. P. Phys. Rev. B 1986, 33, 8822
78. Glendenning, E. D.; Badenhoop, J. K.; Reed, A. E.; Carpenter, J. E.; Bohmann, J. A.; Morales, C. M.; Weinhold, F. NBO Version 5.0; Theoretical Chemistry Institute, University of Wisconsion: Madison, WI, 2001.
79. Bohmann, J. A.; Weinhold, F.; Farrar, T. C. J. Chem. Phys. 1997, 107, 1173
80. Buchwald, S. L.; Nielsen, R. B. Chem. Rev. 1988, 88, 1047
81. Hughes, R. P.; Laritchev, R. B.; Williamson, A.; Incarvito, C. D.; Zakharov, L. N.; Rheingold, A. L. Organometallics 2002, 21, 4873
82. Retbøll, M.; Edwards, A. J.; Rae, A. D.; Willis, A. C.; Bennett, M. A.; Wenger, E. J. Am. Chem. Soc. 2002, 124, 8348
83. Neithamer, D. R.; Parkanyi, L.; Mitchell, J. F.; Wolczanski, P. T. J. Am. Chem. Soc. 1988, 110, 4421
84. Arndt, S.; Elvidge, B. R.; Zeimentz, P. M.; Spaniol, T. P.; Okuda, J. Organometallics 2006, 25, 793
85. Krut'ko, D. P.; Kirsanov, R. S.; Belov, S. A.; Borzov, M. V.; Churakov, A. V.; Howard, J. A. K. Polyhedron 2007, 26, 2864
86. Zhu, G.; Tanski, J. M.; Churchill, D. G.; Janak, K. E.; Parkin, G. J. Am. Chem. Soc. 2002, 124, 13658
87. Bradley, C. A.; Lobkovsky, E.; Chirik, P. J. J. Am. Chem. Soc. 2003, 125, 8110
88. Spannenberg, A.; Jager-Fiedler, U.; Arndt, P.; Rosenthal, U. Z. Kristallogr.-New Cryst. Struct. 2005, 220, 253
89. Jordan, R. F.; Taylor, D. F.; Baenziger, N. C. Organometallics 1990, 9, 1546
90. Scott, J.; Basuli, F.; Fout, A. R.; Huffman, J. C.; Mindiola, D. J. Angew. Chem., Int. Ed. 2008, 47, 8502
91. Ozerov, O. V.; Pink, M.; Watson, L. A.; Caulton, K. G. J. Am. Chem. Soc. 2004, 126, 2105
92. Kraft, B. M.; Lachicotte, R. J.; Jones, W. D. Organometallics 2002, 21, 727
93. Hughes, R. P.; Williamson, A.; Sommer, R. D.; Rheingold, A. L. J. Am. Chem. Soc. 2001, 123, 7443
94. Hughes, R. P.; Laritchev, R. B.; Williamson, A.; Incarvito, C. D.; Zakharov, L. N.; Rheingold, A. L. Organometallics 2002, 21, 4873
95. The arguments put forward in the previous paragraphs suggest that the neighboring group effect should favor activation at the 2-position if phosphine-assisted pathways prevail over oxidative addition. Why, then, do we observe activation at the 4- rather than 2-position for the corresponding reactions with platinum, where both computational and experimental evidence confirms a prominent role for metallophosphoranes- The transition-state structure for activation at the 2-position does indeed show evidence for neighboring group participation by nitrogen, albeit not as conspicuous as in the nickel analogue (Pt?N = 2.35 Å, Ni?N 1.98 Å), probably because the greater stability of the Pt(II) oxidation state reduces the need for donation of electron density from the pyridyl ligand. Moreover, the Pt?C bonds (which are fully formed at the transition state) are very strong, and this favors activation in the 4-position. Thus the rather weak neighboring group effect in the platinum system is unable to overcome the intrinsic preference for activation at the 4-position dictated by the M?C bond strength.