Stabilization of reactive organometallic intermediates inside a self-assembled nanoscale host

Angewandte Chemie - International Edition

Volumn 45, Issue 5, 2006, Pages 745-748

  Fiedler, Dorothea ^a   Bergman, Robert G ^a   Raymond, Kenneth N ^a  

^a UNIVERSITY OF CALIFORNIA   (United States)

Author keywords

Cage compounds; Host guest systems; Reactive intermediates; Ruthenium

Indexed keywords

CAGE COMPOUNDS; HOST-GUEST SYSTEMS; REACTIVE INTERMEDIATES;

COMPLEXATION; MOLECULAR STRUCTURE; NANOSTRUCTURED MATERIALS; RUTHENIUM; SELF ASSEMBLY; SUPRAMOLECULAR CHEMISTRY;

ORGANOMETALLICS;

GADOLINIUM; NANOMATERIAL; ORGANOMETALLIC COMPOUND; RUTHENIUM;

ARTICLE; CHEMISTRY; METHODOLOGY; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; POROSITY; SENSITIVITY AND SPECIFICITY; STANDARD;

GADOLINIUM; MAGNETIC RESONANCE SPECTROSCOPY; NANOSTRUCTURES; ORGANOMETALLIC COMPOUNDS; POROSITY; REFERENCE STANDARDS; RUTHENIUM; SENSITIVITY AND SPECIFICITY;

EID: 31444451082     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200501938     Document Type: Article

References (34)

1. D. J. Cram aptly described the interior of such molecules as an "inner phase"; for example, see: D. J. Cram, Nature 1992, 356, 29.
2. Separation of these kinetic and thermodynamic phenomena may be difficult.
3. D. J. Cram, M. E. Tanner, R. Thomas, Angew. Chem. 1991, 103, 1048;
4. Angew. Chem. Int. Ed. Engl. 1991, 30, 1024.
5. R. Warmuth, Angew. Chem. 1997, 109, 1406;
6. Angew. Chem. Int. Ed. Engl. 1997, 36, 1347.
7. R. Warmuth, M. A. Marvel, Angew. Chem. 2000, 112, 1168;
8. Angew. Chem. Int. Ed. 2000, 39, 1117.
9. M. Yoshizawa, T. Kusukawa, M. Fujita, K. Yamaguchi. J. Am. Chem. Soc. 2000, 122, 6311.
10. M. Yoshizawa, T. Kusukawa, M. Fujita, S. Sakamoto, K. Yamaguchi, J. Am. Chem. Soc. 2001, 123, 10454.
11. S. Körner, F. C. Tucci, D. M. Rudkevich, T. Heinz, J. Rebek, Jr., Chem. Eur. J. 2000, 6, 187.
12. D. L., Caulder, R. E. Powers, T. N. Parac, K. N. Raymond, Angew. Chem. 1998, 110, 1940;
13. Angew. Chem. Int. Ed. 1998, 37, 1840.
14. D. L. Caulder, K. N. Raymond, J. Chem. Soc. Dalton Trans. 1999, 1185.
15. D. L. Caulder, C. Brückner, R. E. Powers, S. König, T. N. Parac, J. A. Leary, K. N. Raymond, J. Am. Chem. Soc. 2001, 123, 8923.
16. T. N. Parac, D. L. Caulder, K. N. Raymond, J. Am. Chem. Soc. 1998, 120, 8003.
17. D. H. Leung, D. Fiedler, R. G. Bergman, K. N. Raymond, Angew. Chem. 2004, 116, 981;
18. Angew. Chem. Int. Ed. 2004, 43, 963.
19. D. Fiedler, D. Pagliero, J. L. Brumaghim, R. G. Bergman, K. N. Raymond, Inorg. Chem. 2004, 43, 846.
20. D. Fiedler, D. H. Leung, R. G. Bergman, K. N. Raymond, J. Am. Chem. Soc. 2004, 126, 3674.
21. M. Ziegler, J. L. Brumaghim, K. N. Raymond, Angew. Chem. 2000, 112, 4285;
22. Angew. Chem. Int. Ed. 2000, 39, 4119.
23. J. L. Brumaghim, M. Michels, K. N. Raymond, Eur. J. Org. Chem. 2004, 4552.
24. B. M. Trost, F. D. Toste, A. B. Pinkerton, Chem. Rev. 2001, 101, 2067.
25. 6 system are readily identified by a strong upfield shift of their resonances.
26. 3] (with one of the four fluorine atoms coordinated to the Ru center). This complex is stable up to 0°C. At this point, formation of 1 starts, along with decomposition to the cyclooctatriene complex, and a weak hydride signal at δ = -12.3 ppm is also observed. A possible mechanism for the formation of 1 starts with insertion of the metal into a methylene C-H bond; hydride migration gives rise to 9-ruthenal(IV)bicyclo[4.2.1]-2-nonene and reductive decyclization leads to the product (also, see the Supporting Information).
27. 2.
28. M. O. Albers, D. J. Robinson, A. Shaver, E. Singleton, Organometallics 1986, 5, 2199.
29. K. Masuda, K. Nakano, T. Fukahori, H. Nagashima, K. Itoh, J. Organomet. Chem. 1992, 428, C21.
30. K. Itoh, K. Masuda, T. Fukahori, K. Nakano, K. Aoki, H. Nagashima, Organometallics 1994, 13, 1020.
31. M. Crocker, M. Green, C. E. Morton, K. R. Nagle, A. G. Orpen, J. Chem. Soc. Dalton Trans. 1985, 2145.
32. A. V. Davis, K. N. Raymond, J. Am. Chem. Soc. 2005, 127, 7912.
33. Hupp and co-workers, for example, demonstrated that encapsulation of a manganese epoxidation catalyst significantly increased the catalyst lifetime: M. L. Merlau, M. P. Mejia, S. T. Nguyen, J. T. Hupp, Angew. Chem. 2001, 113, 4369;
34. Angew. Chem. Int. Ed. 2001, 40, 4239.