Stable mononuclear organometallic Pd(III) complexes and their C-C bond formation reactivity

Journal of the American Chemical Society

Volumn 132, Issue 21, 2010, Pages 7303-7305

  Khusnutdinova, Julia R ^a   Rath, Nigam P ^b   Mirica, Liviu M ^a  

^a WASHINGTON UNIVERSITY   (United States)

^b UNIVERSITY OF MISSOURI ST LOUIS   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

C-C BOND FORMATION; DINUCLEAR; PD COMPLEX; SYNTHESIS AND CHARACTERIZATION; TETRADENTATE LIGANDS;

CHELATION; CHEMICAL BONDS; CYCLIC VOLTAMMETRY; ELECTROCHEMICAL OXIDATION; ETHANE; MAGNETIC MOMENTS; ORGANOMETALLICS; PALLADIUM; SYNTHESIS (CHEMICAL); X RAY DIFFRACTION;

PALLADIUM COMPOUNDS;

PALLADIUM COMPLEX;

ARTICLE; CHEMICAL BINDING; ELECTROLYSIS; ELIMINATION REACTION; MAGNETISM; OXIDATION; SYNTHESIS;

EID: 77952800708     PISSN: 00027863     EISSN: 15205126     Source Type: Journal    
DOI: 10.1021/ja103001g     Document Type: Article

References (66)

1. Negishi, E. Handbook of Organopalladium Chemistry for Organic Synthesis; John Wiley & Sons: Hoboken, NJ, 2002.
2. Henry, P. M. Palladium Catalyzed Oxidation of Hydrocarbons; D. Reidel: Boston, 1980.
3. Muniz, K. Angew. Chem., Int. Ed. 2009, 48, 9412
4. Canty, A., J. J. Chem. Soc., Dalton Trans. 2009, 10409
5. Lyons, T. W. and Sanford, M. S. Chem. Rev. 2010, 110, 1147
6. Powers, D. C., Geibel, M. A. L., Klein, J., and Ritter, T. J. Am. Chem. Soc. 2009, 131, 17050
7. Powers, D. C. and Ritter, T. Nat. Chem. 2009, 1, 302
8. Deprez, N. R. and Sanford, M. S. J. Am. Chem. Soc. 2009, 131, 11234
9. Lanci, M. P., Remy, M. S., Kaminsky, W., Mayer, J. M., and Sanford, M. S. J. Am. Chem. Soc. 2009, 131, 15618
10. Boisvert, L., Denney, M. C., Kloek Hanson, S., and Goldberg, K. I. J. Am. Chem. Soc. 2009, 131, 15802
11. Manolikakes, G. and Knochel, P. Angew. Chem., Int. Ed. 2009, 48, 205
12. Cotton, F. A., Koshevoy, I. O., Lahuerta, P., Murillo, C. A., Sanau, M., Ubeda, M. A., and Zhao, Q. J. Am. Chem. Soc. 2006, 128, 13674
13. Blake, A. J., Gordon, L. M., Holder, A. J., Hyde, T. I., Reid, G., and Schroder, M. J. Chem. Soc., Chem. Commun. 1988, 1452
14. Blake, A. J., Holder, A. J., Hyde, T. I., and Schroder, M. J. Chem. Soc., Chem. Commun. 1987, 987
15. 3- species which is formed under extreme conditions: Tressaud, A., Khairoun, S., Dance, J. M., and Hagenmuller, P. Z. Anorg. Allg. Chem. 1984, 517, 43
16. Meneghetti, S. P., Lutz, P. J., and Kress, J. Organometallics 2001, 20, 5050
17. See Supporting Information.
18. Coulometry measurements confirm that both oxidations correspond to one electron processes.
19. 4) needed to stabilize the distorted octahedral geometry of Pd(III).
20. Spin integration of the EPR spectra vs a Cu standard confirms the formation of the Pd(III) species in more than 95% yield.
21. +, using the B3LYP/CEP-31G(d) functional/basis set combination (see Supporting Information).
22. Detailed DFT and TD-DFT computational studies are ongoing.
23. + was heated in the dark at 51 °C for 65 h.
24. Samples were irradiated with either two 100 W halogen lamps or a 450 W medium pressure mercury lamp.
25. The theoretical yield of ethane is 50% (ref 12).
26. + (5 ± 1%) was also formed.
27. Yagyu, T., Hamada, M., Osakada, K., and Yamamoto, T. Organometallics 2001, 20, 1087
28. Grushin, V. V. and Marshall, W. J. J. Am. Chem. Soc. 2009, 131, 918
29. Ackerman, L. J., Sadighi, J. P., Kurtz, D. M., Labinger, J. A., and Bercaw, J. E. Organometallics 2003, 22, 3884
30. Remy, M. S., Cundari, T. R., and Sanford, M. S. Organometallics 2010, 29, 1522
31. Martin, G. A. and Mirodatos, C. Fuel Process. Technol. 1995, 42, 179
32. Stoukides, M. Res. Chem. Intermed. 2006, 32, 187
33. Olah, G. A. Acc. Chem. Res. 1987, 20, 422
34. Perkins, D. C. L., Puddephatt, R. J., and Tipper, C. F. H. J. Organomet. Chem. 1979, 166, 261
35. Hill, R. H. and Puddephatt, R. J. Organometallics 1983, 2, 1472
36. Kim, J. S., Sen, A., Guzei, I. A., Siable-Sand, L. M., and Rheingold, A. L. J. Chem. Soc., Dalton Trans. 2002, 4726
37. Aerobic homolysis of Co-Me in methylcobalamin gives oxygenated products arising from MeOO reactivity, whereas anaerobic photolysis yields ethane and methane.
38. Hogenkamp, H. P. C. Biochemistry 1966, 5, 417
39. Schrauzer, G. N., Sibert, J. W., and Windgassen, R. J. J. Am. Chem. Soc. 1968, 90, 6681
40. -1.
41. Van Leeuwen, P. W. N. M. J. Organomet. Chem. 1981, 209, 169
42. Bowry, V. W. and Ingold, K. U. J. Am. Chem. Soc. 1992, 114, 4992
43. Thomas, J. K. J. Phys. Chem. 1967, 71, 1919
44. Neta, P., Grodkowski, J., and Ross, A. B. J. Phys. Chem. Ref. Data 1996, 25, 709
45. Van Leeuwen, P. W. N. M., Roobeek, C. F., and Huis, R. J. Organomet. Chem. 1977, 142, 233
46. Hux, J. E. and Puddephatt, R. J. J. Organomet. Chem. 1992, 437, 251
47. Dimerization of two Me radicals to yield ethane is unlikely given the appreciable yields of ethane formed even in the presence of H-donors (ref 5).
48. Shaham, N., Masarwa, A., Matana, Y., Cohen, H., and Meyerstein, D. Eur. J. Inorg. Chem. 2002, 87
49. Sauer, A., Cohen, H., and Meyerstein, D. Inorg. Chem. 1988, 27, 4578
50. -1) have been extensively studied.
51. Kochi, J. K. Acc. Chem. Res. 1974, 7, 351
52. Espenson, J. H. Acc. Chem. Res. 1992, 25, 222
53. Masarwa, A. and Meyerstein, D. Adv. Inorg. Chem. 2004, 55, 271 and ref 30
54. + and a black precipitate were also observed, suggesting a subsequent reductive reaction at a Pd(II) center.
55. -1 (Hawari, J. A., Engel, P. S., and Griller, D. Int. J. Chem. Kinet. 1985, 17, 1215),-
56. -1, ref 30).
57. An alternate mechanism involving dinuclear complexes (ref 3) is unlikely due to steric hindrance imposed by the bulky N4 ligand.
58. Johansson, L., Ryan, O. B., Romming, C., and Tilset, M. Organometallics 1998, 17, 3957
59. Canty, A. J., Denney, M. C., Skelton, B. W., and White, A. H. Organometallics 2004, 23, 1122
60. Canty, A. J., Denney, M. C., Koten, G. v., Skelton, B. W., and White, A. H. Organometallics 2004, 23, 5432
61. Byers, P. K. and Canty, A. J. J. Chem. Soc., Chem. Commun. 1988, 639
62. Byers, P. K., Canty, A. J., Skelton, B. W., Traill, P. R., Watson, A. A., and White, A. H. Organometallics 1992, 11, 3085
63. Kinetic studies are currenty being employed to decipher the mechanism of the homocoupling reactions.
64. Pourreau, D. B. and Geoffroy, G. L. In Advances in Inorganic Chemistry, Vol. 24; Stone, F. G. A. and West, R., Eds.; Academic Press: Orlando, FL, 1985; p 249.
65. Dick, A. R., Kampf, J. W., and Sanford, M. S. J. Am. Chem. Soc. 2005, 127, 12790
66. Canty, A. J. Acc. Chem. Res. 1992, 25, 83