C - H activation by platinum(II): What do gas-phase studies tell us about the solution-phase mechanism?

Organometallics

Volumn 25, Issue 4, 2006, Pages 805-808

  Labinger, Jay A ^a   Bercaw, John E ^a   Tilset, Mats ^b  

^a CALIFORNIA INSTITUTE OF TECHNOLOGY   (United States)

^b UNIVERSITY OF OSLO   (Norway)

Author keywords

[No Author keywords available]

Indexed keywords

GAS-PHASE; SOLUTION-PHASE MECHANISMS; TRANSITION STATE;

BENZENE; CHEMICAL ACTIVATION; ISOMERS; ISOTOPES; ORGANIC SOLVENTS; PLATINUM; SOLUTIONS;

ORGANOMETALLICS;

EID: 33644521782     PISSN: 02767333     EISSN: None     Source Type: Journal    
DOI: 10.1021/om0502638     Document Type: Article

References (15)

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2. (b) Johansson, L.; Tilset, M.; Labinger, J. A.; Bercaw, J. E. J. Am. Chem. Soc. 2000, 122, 10846-10855.
3. (c) Johansson, L.; Tilset, M. J. Am. Chem. Soc. 2001, 123, 739-740.
4. (d) Johansson, L.; Ryan, O. B.; Rømming, C.; Tilset, M. J. Am. Chem. Soc. 2001, 123, 6579-6590.
5. (e) Zhong, H. A.; Labinger, J. A.; Bercaw, J. E. J. Am. Chem. Soc. 2002, 124, 1378-1399.
6. Gerdes, G.; Chen, P. Organometallics 2003, 22, 2217-2225.
7. Anhydrous solutions of B can be prepared by an alternate route (Heyduk, A. F.; Driver, T. G.;. Labinger, J. A.; Bercaw, J. E. J. Am. Chem. Soc. 2004, 126, 15034-15035) and exhibit the enhanced reactivity toward C-H activation predicted from the BLT mechanistic picture.
8. GC do not address this case. Indeed, from comments in their paper it is not at all clear whether they even recognized that there are two different cases.
9. An analogous species has been characterized crystallographically in a different system: Reinartz, S.; White, P. S.; Brookhart, M.; Templeton, J. L. J. Am. Chem. Soc. 2001, 123, 12724-12725.
10. Romeo, R. Comments Inorg. Chem. 1990, 11, 21-57.
11. Procelewska, J.; Zahl, A.; van Eldik, R.; Zhong, H. A.; Labinger, J. A.; Bercaw, J. E. Inorg. Chem. 2002, 41, 2808-2810.
12. GC include an additional intermediate between B and D, corresponding to the five-coordinate species obtained by adding benzene to B. However, that species might instead be a transition state, which would amount to an associative interchange rather than a "true" associative mechanism. All arguments (on both sides) apply equally well to either case; thus, we have left it out in the interests of simplicity.
13. See for example: Tobe, M. L.; Burgess, J. Inorganic Reaction Mechanisms; Addison-Wesley Longman: New York, 1999; pp 74-79.
14. Holtcamp, M. W.; Labinger, J. A.; Bercaw, J. E. J. Am. Chem. Soc. 1997, 119, 848-849.
15. Labinger, J. A.; Osborn, J. A.; Coville, N. J. Inorg. Chem. 1980, 19, 3236-3243.