"Inverse-electron-demand" ligand substitution in palladium(0)-olefin complexes

Journal of the American Chemical Society

Volumn 125, Issue 1, 2003, Pages 12-13

  Stahl, Shannon S ^a   Thorman, Joseph L ^a   De Silva, Namal ^a   Guzei, Ilia A ^a   Clark, Robert W ^a  

^a UNIVERSITY OF WISCONSIN MADISON   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

2,9 DIMETHYL 4,7 DIPHENYL 1,10 PHENANTHROLINE; ALKENE; CARBON; OXYGEN; PALLADIUM; PALLADIUM COMPLEX; PHENANTHROLINE DERIVATIVE; UNCLASSIFIED DRUG;

ARTICLE; CARBONYLATION; CATALYSIS; CHEMICAL ANALYSIS; CHEMICAL REACTION; CHEMICAL STRUCTURE; ELECTROCHEMISTRY; NUCLEAR MAGNETIC RESONANCE; ROOM TEMPERATURE; SUBSTITUTION REACTION;

EID: 0037425533     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja028738z     Document Type: Article

References (25)

1. (a) Heck, R. F. Palladium Reagents in Organic Syntheses; Academic Press: Orlando, 1985.
2. (b) Tsuji, J. Palladium Reagents and Catalysts; Wiley: New York, 1995.
3. (a) Henry, P. M. Palladium Catalyzed Oxidation of Hydrocarbons; Kluwer: Boston, 1980.
4. (b) For a specific recent example, see: ten Brink. G.-J.; Arends, I. W. C. E.; Sheldon, R. A. Science 2000, 287, 1636-1639.
5. (a) Stahl, S. S.; Thorman, J. L.; Nelson, R. C.; Kozee, M. A. J. Am. Chem. Soc. 2001, 123, 7188-7189.
6. (b) Steinhoff, B. A.; Fix, S. R.; Stahl, S. S. J. Am. Chem. Soc. 2002, 124, 766-767.
7. (a) Ozawa, F.; Ito, T.; Nakamura, Y.; Yamamoto, A. J. Organomet. Chem. 1979, 168, 375-391.
8. (b) van Asselt, R.; Elsevier, C. J.; Smeets, W. J. J.; Spek, A. L. Inorg. Chem. 1994, 33, 1521-1531.
9. (c) Canovese, L.; Visentin, F.; Uguagliati, P.; Crociani, B. J. Chem. Soc., Dalton Trans. 1996, 1921-1926.
10. (d) Canovese, L.; Visentin, F.; Chessa, G.; Uguagliati, P.; Dolmella, A. J. Organomet. Chem. 2000, 601, 1-15.
11. See ref 4 and Halpern, J.; Weil, T. A. J. Chem. Soc., Chem. Commun. 1973, 631-632.
12. For leading references describing similar equilibrium electronic effects for other zerovalent, group 10 olefin complexes, see: (a) Otsuka, S.; Yoshida, T.; Tatsuno, Y. J. Am. Chem. Soc. 1971, 93, 6462-6469.
13. (b) Tolmam, C. A. J. Am. Chem. Soc. 1974, 96, 2780-2789.
14. (c) Ittel, S. D.; Ibers, J. A. Adv. Organomet. Chem. 1976, 14, 33.
15. (d) Ittel, S. D. Inorg. Chem. 1977, 16, 2589-2597.
16. This nomenclature is borrowed from the frontier-orbital description of Diels-Alder and related cycloaddition reactions: Fleming, I. Frontier Orbitals and Organic Chemical Reactions; Wiley: New York, 1976.
17. (a) Langford, C. H.; Gray, H. B. Ligand Substitution Processes; W. A. Benjamin: New York, 1965.
18. Basolo, F.; Pearson, R. G. Mechanisms of Inorganic Reactions; 2nd Ed.; Wiley: New York, 1967.
19. Pt. See, for example: (a) Pearson, R. G.; Gray, H. B.; Basolo, F. J. Am. Chem. Soc. 1960, 82, 787-792.
20. (b) Gray, H. B. J. Am. Chem. Soc. 1962, 84, 1548-1552.
21. (c) Belluco, U.; Cattalini, L.; Turco, A. J. Am. Chem. Soc. 1964, 86, 226-229.
22. The following reference states explicitly that such "electrophilic" ligand substitution pathways are unknown, and we are unaware of any subsequent precedent. Collman, J. P.; Hegedus, L. S.; Norton, J. R.; Finke, R. G. Principles and Applications of Organotransition Metal Chemistry; 2nd ed.; University Science Books: Mill Valley, CA, 1987; p 238.
23. Anomalous electronic effects observed recently in ligand substitution reactions of electrophilic platinum(II) and iridium(III) complexes have been attributed to ground-state stabilization effects. The mechanism in these cases remains consistent with attack of a nucleophilic ligand on an electrophilic metal center. (a) Zhong, H. A.; Labinger, J. A.; Bercaw, J. E. J. Am. Chem. Soc. 2002, 124, 1378-1399.
24. (2) Tellers, D. M.; Yung, C. M.; Arndtsen, B. A.; Adamson, D. R.; Bergman, R. G. J. Am. Chem. Soc. 2002, 124, 1400-1410.
25. Reference 10, Chapter 5.