O2 insertion into a palladium(II)-hydride bond: Observation of mechanistic crossover between HX-reductive-elimination and hydrogen-atom-abstraction pathways

Chemical Science

Volumn 2, Issue 2, 2011, Pages 326-330

  Konnick, Michael M ^a   Decharin, Nattawan ^a   Popp, Brian V ^a   Stahl, Shannon S ^a  

^a UNIVERSITY OF WISCONSIN MADISON   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

AEROBIC OXIDATIONS; ATOM ABSTRACTION; COMPUTATIONAL STUDIES; ELECTRON-DONATING; ELECTRON-RICH; ELECTRONWITHDRAWING; HAMMETT PLOTS; INSERTION REACTIONS; KINETIC STUDY; NON-LINEAR; PARALLEL MECHANISMS; RATE LIMITING; REDUCTIVE ELIMINATION;

ABSTRACTING; CARBOXYLIC ACIDS; HYDROGEN; LIGANDS; MECHANISMS; MOLECULAR OXYGEN; OXYGENATION; PALLADIUM COMPOUNDS;

REACTION RATES;

EID: 79954481454     PISSN: 20416520     EISSN: 20416539     Source Type: Journal    
DOI: 10.1039/c0sc00392a     Document Type: Article

References (48)

1. R. A. Sheldon, I. W. C. E. Arends, G. J. Ten Brink and A. Dijksman, Acc. Chem. Res., 2002, 35, 774-781
2. S. S. Stahl, Angew. Chem., Int. Ed., 2004, 43, 3400-3420
3. T. Nishimura and S. Uemura, Synlett, 2004, 201-216
4. S. S. Stahl, Science, 2005, 309, 1824-1826
5. M. S. Sigman and D. R. Jensen, Acc. Chem. Res., 2006, 39, 221-229
6. K. M. Gligorich and M. S. Sigman, Chem. Commun., 2009, 3854- 3867
7. X. Chen, K. M. Engle, D.-H. Wang and J.-Q. Yu, Angew. Chem., Int. Ed., 2009, 48, 5094-5115.
8. S. S. Stahl, J. L. Thorman, R. C. Nelson and M. A. Kozee, J. Am. Chem. Soc., 2001, 123, 7188-7189
9. C. R. Landis, C. M. Morales and S. S. Stahl, J. Am. Chem. Soc., 2004, 126, 16302-16303;
10. M. M. Konnick, I. A. Guzei and S. S. Stahl, J. Am. Chem. Soc., 2004, 126, 10212-10213;
11. M. M. Konnick, B. A. Gandhi, I. A. Guzei and S. S. Stahl, Angew. Chem., Int. Ed., 2006, 45, 2904-2907
12. B. V. Popp and S. S. Stahl, J. Am. Chem. Soc., 2007, 129, 4410-4422
13. B. V. Popp, J. E. Wendlandt, C. R. Landis and S. S. Stahl, Angew. Chem., Int. Ed., 2007, 46,601-604
14. M. M. Konnick and S. S. Stahl, J. Am. Chem. Soc., 2008, 130, 5753-5762
15. B. V. Popp and S. S. Stahl, Chem.-Eur. J., 2009, 15, 2915-2922;
16. B. V. Popp, C. M. Morales, C. R. Landis and S. S. Stahl, Inorg. Chem., 2010, 49, 8200-8207.
17. J. M. Keith, R. J. Nielsen, J. Oxgaard and W. A. Goddard, J. Am. Chem. Soc., 2005, 127, 13172-13179
18. M. C. Denney, N. A. Smythe, K. L. Cetto, R. A. Kemp and K. I. Goldberg, J. Am. Chem. Soc., 2006, 128, 2508-2509
19. J. M. Keith, R. P. Muller, R. A. Kemp, K. I. Goldberg, W. A. Goddard, and J. Oxgaard, Inorg. Chem., 2006, 45, 9631-9633
20. J. M. Keith, W. A. Goddard, and J. Oxgaard, J. Am. Chem. Soc., 2007, 129, 10361-10369
21. S. Chowdhury, I. Rivalta, N. Russo and E. Sicilia, Chem. Phys. Lett., 2007, 443, 183-189
22. S. Chowdhury, I. Rivalta, N. Russo and E. Sicilia, J. Chem. Theory Comput., 2008,4, 1283-1292
23. S. Chowdhury, I. Rivalta, N. Russo and E. Sicilia, Chem. Phys. Lett., 2008, 456, 41-46;
24. E. A. Katayev, H. V. Lavrova and V. N. Khrustaleva, J. Porphyrins Phthalocyanines, 2008, 12, 1137- 1145;
25. J. M. Keith, California Institute of Technology, Pasadena, California, 2008, p. 117
26. J. M. Keith and W. A. Goddard, J. Am. Chem. Soc., 2009, 131, 1416-1425.
27. J. Muzart and J. P. Pete, J. Mol. Catal., 1982, 15, 373-376
28. K. Takehira, T. Hayakawa, H. Orita and M. Shimizu, J. Mol. Catal., 1989, 53, 15-21
29. T. Hosokawa and S. Murahashi, Acc. Chem. Res., 1990, 23, 49-54
30. T. Hosokawa, T. Nakahira, M. Takano and S. Murahashi, J. Mol. Catal., 1992, 74, 489-498
31. T. Nishimura, T. Onoue, K. Ohe and S. Uemura, J. Org. Chem., 1999, 64, 6750-6755
32. T. Nishimura, N. Kakiuchi, T. Onoue, K. Ohe and S. Uemura, J. Chem. Soc, Perkin Trans. 1, 2000, 1915-1918.
33. J. H. Bayston and M. E. Winfield, J. Catal, 1964, 3, 123-128
34. T. T. Wenzel, Stud. Surf. Sci. Catal, 1991, 66, 545-554
35. A. Bakac, J. Am. Chem. Soc, 1997, 119, 10726-10731
36. D. D. Wick and K. I. Goldberg, J. Am. Chem. Soc, 1999, 121, 11900-11901
37. A. Bakac, J. Photochem. Photobiol, A, 2000, 132, 87-89
38. S. Thyagarajan, C. D. Incarvito, A. L. Rheingold and K. H. Theopold, Chem. Commun., 2001, 2198-2199;
39. W. Cui and B. B. Wayland, J. Am. Chem. Soc, 2006, 128, 10350-10351
40. M. Schlangen and H. Schwarz, Helv. Chim. Acta, 2008, 91, 379-386
41. J. L. Look, D. D. Wick, J. M. Mayer and K. I. Goldberg, Inorg. Chem., 2009, 48, 1356-1369
42. E. Szajna- Fuller and A. Bakac, Inorg. Chem., 2010, 49, 781-785.
43. The oxygenation rates were determined by the method of initial rates. We have shown previously that hydrogen bond donors, including the Pd-OOH product, accelerate the rate of oxygenation and lead to non-exponential decay of the Pd-H species in reactions of this type. For further discussion and characterization of this effect, see: ref. 2g.
44. 2CC6H4OMe), was synthesized through an established literature procedure from tetrabutylammonium hydroxide and para-methoxybenzoic acid: Y. Sato, H. Fujisawa and T. Mukaiyama, Chem. Lett., 2005, 34, 1188-1189.
45. 2]-dependence HAA pathway becomes much more pronounced at lower temperatures, as implied by the Hammett plot in Fig. 2. Note
46. Computational method: All computations were performed with the Gaussian 03 program. Geometry optimizations were performed using the B3LYP functional with the Stuttgart RSC 1997 ECP basis set for Pd and 6-31G for all other atoms. Spin-unrestricted methodology was used for the calculations. At the calculated stationary points, solvation-corrected single-point-energy calculations were carried out with the Pd basis detailed above and the 6-311G basis for all other atoms. These calculations were used to predict the solvation free energy close to experimental conditions (toluene solvent at 50 °C). Note
47. 1). See ref. 2e for further details. Note
48. ‡ values (Figs. S3 and S4). The scatter introduced by the calculated ΔS‡ values is also cancelled in the plot of ΔΔG‡ vs. p (Fig. 5B). See the supplementary information for details Note