Carbon-carbon bond activation of 2,2,6,6-tetramethyl-piperidine-1-oxyl by a RhII metalloradical: A combined experimental and theoretical study

Journal of the American Chemical Society

Volumn 130, Issue 6, 2008, Pages 2051-2061

  Kin, Shing Chan ^a   Xin, Zhu Li ^a   Dzik, Wojciech I ^b   De Bruin, Bas ^b  

^a CHINESE UNIVERSITY OF HONG KONG   (Hong Kong)

^b UNIVERSITY OF AMSTERDAM   (Netherlands)

Author keywords

[No Author keywords available]

Indexed keywords

BOND ACTIVATION; ELECTRON TRANSFER; IONIC PATHWAY; NUCLEOPHILIC SUBSTITUTION ATTACK;

CHARGE TRANSFER; DENSITY FUNCTIONAL THEORY; REACTION KINETICS;

CHEMICAL BONDS;

2,2,6 TRIMETHYL 2,3,4,5 TETRAHYDRO 1 PYRIDINIUMOLATE; 2,2,6,6 TETRAMETHYLPIPERIDIN 1 OL; 2,2,6,6 TETRAMETHYLPIPERIDINE 1 OXYL; ANION; CARBON; CATION; HYDROGEN; METHYL GROUP; PIPERIDINE DERIVATIVE; PORPHYRIN DERIVATIVE; PYRIDINIUM DERIVATIVE; RHODIUM; RHODIUM MESO TETRAMESITYLPORPHYRIN; UNCLASSIFIED DRUG;

ACCURACY; ARTICLE; ATOM; CHEMICAL BOND; CHEMICAL STRUCTURE; DENSITY FUNCTIONAL THEORY; ELECTRON TRANSPORT; ENTROPY; GAS CHROMATOGRAPHY; HIGH TEMPERATURE; KINETICS; MASS SPECTROMETRY; REACTION ANALYSIS; STRUCTURE ANALYSIS;

BINDING SITES; CARBON; CYCLIC N-OXIDES; FREE RADICALS; HYDROGEN; KINETICS; METALLOPORPHYRINS; MODELS, CHEMICAL; MOLECULAR STRUCTURE; RHODIUM;

EID: 39049109813     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja078157f     Document Type: Article

References (86)

1. (a) Crabtree, R. H. Chem. Rev. 1985, 85, 245-269.
2. (b) Murakami, M.; Ito, Y. In Topics in Organometallic Chemistry; Murai, S., Ed.; Springer; Berlin 1999; Vol. 3, pp 97-129.
3. (c) Rybtchinski, B.; Milstein, D. Angew. Chem. Int. Ed. 1999, 38, 870-883.
4. (d) Jun, C.-H. Chem. Soc. Rev. 2004, 33, 610-618.
5. Martinho Simões, J. A.; Beauchamp, J. L. Chem. Rev. 1990, 90, 629-688.
6. Hemond, R. C.; Hughes, R. P.; Locker, H. B. Organometallics 1986, 5, 2391-2392.
7. (a) Rybtchinski, B.; Vigalok, A.; Ben-David, Y.; Milstein, D. J. Am. Chem. Soc. 1996, 118, 12406-12415.
8. (b) Sundermann, A.; Uzan, O.; Milstein, D.; Martin, J. M. L. J. Am. Chem. Soc. 2000, 122, 7095-7104.
9. Brunkan, N. M.; Brestensky, D. M.; Jones, W. D. J. Am. Chem. Soc. 2004, 126, 3627-3641.
10. (a) Cui, W. H.; Wayland, B. B. J. Am. Chem. Soc. 2006, 128, 10350-10351.
11. (b) Cui, W. H.; Wayland, B. B. J. Am. Chem. Soc. 2004, 126, 8266-8274.
12. (c) Cui, W.; Zhang, X. P.; Wayland, B. B. J. Am. Chem. Soc. 2003, 125, 4994-4995.
13. (d) Zhang, X.-X.; Wayland, B. B. J. Am. Chem. Soc. 1994, 116, 7897-7898.
14. (e) Wayland, B. B.; Ba, S.; Sherry, A. E. J. Am. Chem. Soc. 1991, 113, 5305-5311.
15. (f) Sherry, A. E.; Wayland, B. B. J. Am. Chem. Soc. 1990, 112, 1259-1261.
16. (g) Farnos, M. D.; Woods, B. A.; Wayland, B. B. J. Am. Chem. Soc. 1986, 108, 3659-3663.
17. (a) Paonessa, R. S.; Thomas, N. C.; Halpern, J. J. Am. Chem. Soc. 1985, 107, 43333-4335.
18. (b) Chen, M. J.; Rathke, J. W. Organometallics 1994, 13, 4875-4880.
19. For recent overviews, see: (a) Hetterscheid, D. G. H.; Grützmacher, H.; Koekoek, A. J. J.; de Bruin, B. In The Organometallic Chemistry of Rh, Ir, Pd and Pt Based Radicals; Higher Valent Species; Karlin, K. D., Ed.; Vol 55; Wiley: 2007, pp 247-354.
20. (b) de Bruin, B.; Hetterscheid, D. G. H. Eur. J. Inorg. Chem. 2007, 2, 211-230.
21. (a) Hetterscheid, D. G. H.; Klop, M.; Kicken, R. J. N. A. M.; Smits, J. M. M.; Reijerse, E. J.; de Bruin, B. Chem. Eur. J. 2007, 13, 3386-3405.
22. (b) de Bruin, B.; Russcher, J. C.; Grüzmacher, H. J. Organomet. Chem. 2007, 692, 3167-3173.
23. (c) Hetterscheid, D. G. H.; de Bruin, B. J. Mol. Catal. A. Chem., 2006, 251, 291-296.
24. (d) Hetterscheid, D. G. H.; Kaiser, J.; Reijerse, E. J.; Peters, T. P. J.; Thewissen, S.; Blok, A. N. J.; Smits, J. M. M.; de Gelder, R.; de Bruin, B. J. Am. Chem. Soc. 2005, 127, 1895-1905.
25. (e) Hetterscheid, D. G. H.; Bens, M.; de Bruin, B.; Dalton Trans. 2005, 979-984.
26. (f) Knijnenburg, Q.; Horton, A. D.; van der Heijden, H.; Kooistra, T. M.; Hetterscheid, D. G. H.; Smits, J. M. M.; de Bruin, B.; Budzelaar, P. H. M.; Gal, A. W. J. Mol. Catal. A. Chem. 2005, 232, 151-159.
27. (g) Hetterscheid, D. G. H.; Smits, J. M. M.; de Bruin, B. Organometallics. 2004, 23, 4236-4246.
28. (h) de Bruin, B.; Budzelaar, P. H. M.; Gal, A. W.; Angew. Chem., Int. Ed. 2004, 43, 4142-4157.
29. (i) Hetterscheid, D. G. H.; de Bruin, B.; Smits, J. M. M.; Gal, A. W. Organometallics 2003, 22, 3022-3024.
30. (j) de Bruin, B.; Thewissen, S.; Yuen, T.-W.; Peters, T. P. J.; Smits, J. M. M.; Gal, A. W.; Organometallics 2002, 21, 4312-4314.
31. (k) de Bruin, B.; Peters, T. P. J.; Thewissen, S.; Blok, A. N. J.; Wilting, J. B. M.; de Gelder, R.; Smits, J. M. M.; Gal, A. W. Angew. Chem., Int. Ed. 2002, 41, 2135-2138.
32. (l) Willems, S. T. H.; Russcher, J. C.; Budzelaar, P. H. M.; de Bruin, B.; de Gelder, R.; Smits, J. M. M.; Gal, A. W. Chem. Commun. 2002, 148-149.
33. (a) Mak, K. W.; Yeung, S. K.; Chan, K. S. Organometallics 2002, 21, 2362-2364.
34. (b) Tse, M. K.; Chan, K. S. J. Chem. Soc. Dalton Trans. 2001, 510-511.
35. (c) Zhang, L.; Chan, K. S. J. Organomet. Chem. 2006, 691, 3782-3787.
36. (d) Zhang, L.; Chan, K. S. J. Organomet. Chem. 2007, 692, 2021-2027.
37. (e) Chan, K. S.; Li, X. Z.; Fung, C. W.; Zhang, L. Organometallics 2007, 26, 20-21.
38. (f) Chan, K. S.; Li, X. Z.; Fung, C. W.; Zhang, L. Organometallics 2007, 26, 2679-2687.
39. (a) A more stable diphenyl substituted nitrone co-product analogue of 6 has been isolated; see ref 7.
40. (b) Breuer, E.; Aurich, H. G.; Nielsen, A. Nitrones, Nitronates and Nitroxides: Wiley & Sons: New York, 1989.
41. (c) A derivative of azaoxetane 7 has been a proposed, unstable intermediate: Baldwin, J. E.; Bhatnagar, A. K.; Choi, S. C.; Shortridge, T. J. J. Am. Chem. Soc. 1971, 93, 4082-4084.
42. (a) Chan, K. S.; Leung, Y. B. Inorg. Chem. 1994, 33, 3187.
43. (b) Zhang, L.; Chan, K. S. Organometalllics 2007, 26, 679-684.
44. 2-H = 100 kcal/mol, Ph-H = 113 kcal/mol). See: Luo, Y.-R. Handbook of Bond Dissociation Energies in Organic Compounds; CRC Press: Boca Raton, FL, 2003.
45. For a leading reference of PCET, see: Rhile, I. H.; Mayer, J. M. Angew. Chem., Int. Ed. 2005, 44, 1598-1599.
46. 2 and n = 3 or 4).
47. 1-O-(neutral) Rh(II) complex: Felthouse, T. R.; Dong, T.-Y.; Hendrickson, D. N.; Shieh, H.-S.; Thompson, M. R. J. Am. Chem. Soc. 1986, 108, 8201-8214.
48. 1-O(neutral)-Cu(II) complex: Baskett, M.; Lathi, P. M.; Palacio, F. Polyhedron, 2003, 22, 2363-2374.
49. 1-O(neutral)-Ru(II) porphyrin: Selyer, J. W.; Fanwick, P. E.; Leidner, C. R. Inorg. Chem. 1992, 31, 3699-3700.
50. 1-O(anionic)-Si(IV) porphryin: Zheng, J.-Y.; Konishi, K.; Aida, T. J. Am. Chem. Soc. 1998, 120, 9838-9843.
51. 1-O(anionic)-Ti(IV) complex: Mahanthappa, M. K.; Huang, K.-W.; Cole, A. P.; Waymouth, R. M. Chem. Commun. 2002, 502-503.
52. 1-O(anionic)-1r(III) complex: Hetterscheid, D. G. H.; Kaiser, J.; Reijerse, E.; Peters, T. P. J.; Thewissen, S.; Blok, A. N. J.; Smits, J. M. M.; de Gelder, R.; de Bruin, B. J. Am. Chem. Soc. 2005, 127, 1895-1905.
53. 2-ON Sm(III) complex: Evans, W. J.; Perotti, J. M.; Doedens, R. J.; Ziller, J. W. Chem. Commun. 2001, 2326-2327.
54. 2-O(anionic)N-Ni(II) complex: Mindiola, D. J.; Waterman, R.; Jenkins, D. M.; Hillhouse, G. L. Inorg. Chim. Acta 2003, 345, 299-308.
55. 2-O (anionic)N-Ti(IV) complex: ref 16e.
56. 10b
57. Gosh, A. J. Biol. Inorg. Chem. 2006, 11, 712-724.
58. Harvey, J. N.; Poli, R.; Smith, K. M. Coord. Chem. Rev. 2003, 238-239, 347-361.
59. This is not the first time that hybrid HF/DFT functional (such as b3-lyp) are found to overestimate the relative stability of radicals compared to closed-shell systems: (a) Saeys, M.; Reyniers, M.-F.; Marin, G. B.; Van Speybroeck, V.; Waroquir, J. Phys. Chem. A 2003, 107, 9147-9159.
60. (b) Sustmann, R.; Sicking, W.; Huisgen, R.; J. Am. Chem. Soc. 2003, 125, 14425-14434.
61. (c) Jensen, K. P.; Ryde, U.; J. Phys. Chem. A 2003, 107, 7539-7545.
62. (d) Gosh, A.; J. Biol. Inorg. Chem. 2006, 11, 712-724.
63. (a) Ozinskas, A. J.; Bobst, A. M. Helv. Chim. Acta 1980, 63, 1407-1411.
64. (b) Fields, J. D.; Kropp, P. J. J. Org. Chem. 2000, 65, 5937-5941.
65. Wayland, B. B.; Van Voorhees, S. L.; Wilker, C. Inorg. Chem. 1986, 25, 4039-4042.
66. Perkampus H. H. UV-VIS Spectroscopy and Its Applications; Springer-Verlag: Berlin, Heidelberg, 1992.
67. Atkins, P. Physical Chemistry, 6th ed.; Oxford University Press: Oxford, U.K., 1998.
68. (a) Ahlrichs, R; et al. Turbomole, version 5; Theoretical Chemistry Group, University of Karlsruhe: Karlsruhe, Germany, 2002.
69. (b) Treutler, O.; Ahlrichs, R. J. Chem. Phys. 1995, 102, 346-354.
70. (c) Turbomole, version 5, Turbomole basisset library (see ref 25a).
71. (d) Schäfer, A.; Horn, H.; Ahlrichs, R. J. Chem. Phys. 1992, 97, 2571-2577.
72. (e) Andrae, D.; Haeussermann, U.; Dolg, M.; Stall, H.; Preuss, H. Theor. Chim. Acta 1990, 77, 123-141.
73. (f) Schäfer, A.; Huber, C.; Ahlrichs, R. J. Chem. Phys. 1994, 100, 5829-5835.
74. (g) Ahlrichs, R.; May, K. Chem. Phys. 2000, 2, 943.
75. (a) PQS, version 2.4; Parallel Quantum Solutions: Fayetteville, AR, 2001 (the Baker optimizer is available separately from PQS upon request),
76. (b) Baker, J. J. Comput. Chem. 1986, 7, 385-395.
77. (a) Becke, A. D. Phys. Rev. A 1988, 38, 3098-3100.
78. (b) Perdew, J. P. Phys. Rev. B 1986, 33, 8822-8824.
79. (a) Lee, C.; Yang, W.; Parr, R. G. Phys. Rev. B 1988, 37, 785-789.
80. (b) Becke, A. D. J. Chem. Phys. 1993, 98, 1372-1377.
81. (c) Becke, A. D. J. Chem. Phys. 1993, 98, 5648-5652.
82. (d) Calculations were performed using the Turbomole functional "b3-lyp", which is not identical to the Gaussian "B3LYP" functional.
83. Knijnenburg, Q.; Hetterscheid, D.; Kooistra, T. M.; Budzelaar, P. H. M.; Eur. J. Inorg. Chem. 2004, 1204-1211 and references cited therein.
84. Klamt, A.; Schüürmann, G.; J. Chem. Soc., Perkin Trans. 2 1993, 5, 799-805.
85. Spek, A. L. PLATON, A Multipurpose Crystallographic Tool; Utrecht University: Utrecht, The Netherlands, 2003.
86. Schaftenaar, G.; Noordik, J. H. J. Comput.-Aided Mol. Des. 2000, 14 (2), 123-134.