Novel binding modes and hemilability in atropisomeric phosphino-amino palladium complexes

Organometallics

Volumn 23, Issue 9, 2004, Pages 2008-2014

  Faller, J W ^a   Sarantopoulos, Nikos ^a  

^a YALE UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

BIDENTATE LIGAND; ENANTIOMERIC ATROPISOMERS; HEMILABILITY; NOVEL BINDING MODES;

COALESCENCE; DIFFRACTOMETERS; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; PALLADIUM COMPOUNDS; RESONANCE; SINGLE CRYSTALS; TRANSITION METALS; X RAY CRYSTALLOGRAPHY;

ORGANOMETALLICS;

EID: 2442570948     PISSN: 02767333     EISSN: None     Source Type: Journal    
DOI: 10.1021/om030681h     Document Type: Article

References (32)

1. Cyr, P. W.; Rettig, S. J.; Patrick, B. O.; James, B. R. Organometallics 2002, 21, 4672-4679.
2. (a) Kocovsky, P.; Vyskocil, S.; Cisarova, I.; Sejbal, J.; Tislerova, I.; Smrcina, M.; Lloyd-Jones, G. C.; Stephen, S. C.; Butts, C. P.; Murray, M.; Langer, V. J. Am. Chem. Soc. 1999, 121, 7714-7715.
3. (b) Lloyd-Jones, G. C.; Stephen, S. C.; Murray, M.; Butts, C. P.; Vyskocil, S.; Kocovsky, P. Chem. Eur. J. 2000, 6, 4348-4357.
4. (c) Kocovsky, P.; Vyskocil, S.; Smrcina, M. Chem. Rev. 2003, 103, 3213-3245.
5. Dotta, P.; Kumar, A.; Pregosin, P. S.; Albinati, A.; Rizzato, S. Organometallics 2008, 22, 5345-5349.
6. Pathak, D. D.; Adams, H.; Bailey, N. A.; King, P. J.; White, C. J. Organomet. Chem. 1994, 479, 237-245.
7. Feiken, N.; Pregosin, P. S.; Trabesinger, G.; Scalone, M. Organometallics 1997, 16, 537-543.
8. Feiken, N.; Pregosin, P. S.; Trabesinger, G.; Albinati, A.; Evoli, G. L. Organometallics 1997, 16, 5756-5762.
9. Doherty, S.; Newman, C. R.; Hardacre, C.; Nieuwenhuyzen, M.; Knight, J. G. Organometallics 2003, 22, 1452-1462.
10. Bergens, S. H.; Leung, P.-H.; Bosnich, B.; Rheingold, A. L. Organometallics 1990, 9, 2406-2408.
11. Brunkan, N. M.; White, P. S.; Gagne, M. R. J. Am. Chem. Soc. 1998, 120, 11002-11003.
12. Brunkan, N. M.; Gagne, M. R. Organometallics 2002, 21, 4711-4717.
13. (a) Tomori, H.; Fox, J. M.; Buchwald, S. L. J. Org. Chem. 2000, 65, 5334-5341.
14. (b) Shen, X. Q.; Guo, H.; Ding, K. L. Tetrahedron: Asymmetry 2000, 11, 4321-4327.
15. Wang, Y.; Li, X.; Sun, J.; Ding, K. Organometallics 2003, 22, 1856-1862.
16. 18
17. Sprinz, J.; Kiefer, M.; Helmchen, G.; Huttner, G.; Walter, O.; Zsolnai, L.; Reggelin, M. Tetrahedron Lett. 1994, 35, 1523-1526.
18. Steinhagen, H.; Reggelin, M.; Helmchen, G. Angew. Chem., Int. Ed. 1997, 36, 2108-2110.
19. Hayashi, T.; Kawatsura, M.; Uozumi, Y. J. Am. Chem. Soc. 1998, 120, 1681-1687.
20. Sloan, T. E. Stereochemical Nomenclature and Notation in Inorganic Chemistry. Top. Stereochem. 1981, 12, 1-35.
21. Faller, J. W.; Stokes-Huby, H. L.; Albrizzio, M. A. Helv. Chim. Acta 2001, 84, 3031-8042.
22. Elguero, J.; Fruchier, A.; de la Hoz, A.; Jalon, F. A.; Manzano, B. R.; Otero, A.; de la Torre, F. G. Chem. Ber. 1996, 129, 589-594.
23. Elguero, J.; Guerrero, A.; de la Torre, F. G.; de la Hoz, A.; Jalon, F. A.; Manzano, B. R.; Rodriguez, A. New J. Chem. 2001, 25, 1050-1060.
24. 2. Since there is little C=N character in that complex, interconversion of the methyl environments by umbrella inversion could occur via this intermediate, in which the metal would continually be bound to some portion of the dimethylaniline fragment. This would also inhibit atropisomerization in this intermediate.
25. 2.
26. Desponds, O.; Schlosser, M. Tetrahedron Lett. 1998, 37, 47-48.
27. 2 group in 2 relative to that in 1 also supports this assumption. There are also (1) shifts of anti protons to lower field than syn protons and (2) protons cis to phosphine that are to lower field than those trans to phosphine, which are not normally observed.
28. Vedejs, E.; Donde, Y. J. Org. Chem. 2000, 65, 2337-2343.
29. We have found resolutions of this type useful in a number of cases, but this one is not ideal. The formation as a triclinic or orthorhombic phase is random, although it appears that seeding can induce one form. A more critical problem is that the orthorhombic crystals have a propensity for forming racemic twins. Thus, a given crystal will have a nonracemic mixture, but the fraction can vary. For example, a large orthorhombic crystal was cut and the larger portion of the crystal was used for a planned CD experiment; however, the remaining portion which was used for X-ray analysis was a ∼55:45 racemic twin and the crystal showed a very weak dichroism, indicating a nearly racemic mixture. Testing several large crystals by CD gave results which indicated that racemic twinning was common; however, in some crystals the twinning was minimal and the CD could be determined and used as a diagnostic for racemization rate. We are still investigating these phenomena.
30. HKL2000 (Denzo-SMN) software package: Minor, W.; Otwinowski, Z. Processing of X-ray Diffraction Data Collected in Oscillation Mode. In Methods in Enzymology; Carter, C. W., Jr., Sweet, R. M., Eds.; Academic Press: New York, 1997; Vol. 276A (Macromolecular Crystallography), pp 307-326.
31. Altomare, A.; Cascarano, G.; Giacovazzo, C.; Guagliardi, A. J. Appl. Cryatallogr. 1993, 26, 348.
32. TEXSAN for Windows version 1.06: Crystal Structure Analysis Package; Molecular Structure Corp., The Woodlands, TX, 1997-1999.