First synthesis, structure, and reactivity of (acylimino)triaryl-λ5-bismuthanes stabilized by ortho-substituted aryl ligands

Organometallics

Volumn 18, Issue 14, 1999, Pages 2580-2582

  Matano, Yoshihiro ^a   Nomura, Hazumi ^a   Shiro, Motoo ^b   Suzuki, Hitomi ^a  

^a KYOTO UNIVERSITY   (Japan)

^b RIGAKU CORPORATION   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0000006751     PISSN: 02767333     EISSN: None     Source Type: Journal    
DOI: 10.1021/om990252c     Document Type: Article

References (31)

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2. Wittig, G.; Hellwinkel, D. Chem. Ber. 1964, 97, 789.
3. (a) Suzuki, H.; Nakaya, C.; Matano, Y.; Ogawa, T. Chem. Lett. 1991, 105.
4. (b) Suzuki, H.; Ikegami, T. J. Chem. Res., Synop. 1996, 24.
5. Pasenok, S. V.; Kirij, N. V.; Yagupolskii, Y. L.; Naumann, D.; Tyrra, W. J. Fluorine Chem. 1993, 63, 179.
6. Compound A was structurally characterized by X-ray diffraction analysis, where the bismuth center adopts a distorted trigonal bipyramidal geometry with a Bi=N bond length of 2.13(1) Å. The oxazoline group at the ortho position intramolecularly coordinates to the bismuth. Ikegami, T.; Suzuki, H. Organometallics 1998, 17, 1013. (Chemical Equation Presented)
7. 3NO: C, 46.55; H, 3.57; N, 2.36. Found: C, 46.59; H, 3.47; N, 2.09. Compounds 3ab-ca also gave satisfactory spectral and analytical data. See Supporting Information.
8. Kinetic stabilization afforded by ortho-substituted aryl groups has been applied for stabilizing highly reactive functionalities. For example, see: (a) Yoshifuji, M.; Shima, I.; Inamoto, N.; Hirotsu, K.; Higuchi, T. J. Am. Chem. Soc. 1981, 103, 4587.
9. (b) West, R.; Fink, M. J.; Michl, J. Science 1981, 214, 1343.
10. (c) Cowley, A. H.; Kilduff, J. E.; Newman, T. H.; Pakulski, M. J. Am. Chem. Soc. 1982, 104, 5820.
11. (d) Tokitoh, N.; Matsumoto, T.; Manmaru, K.; Okazaki, R. J. Am. Chem. Soc. 1993, 115, 8855.
12. ortno-Methoxy aryl groups have been shown to stabilize the cationic heteroatom thermodynamically. For example, see: (a) McEwen, W. E.; Lau, K. W. J. Org. Chem. 1982, 47, 3595.
13. (b) Wada, M.; Kanzaki, M.; Fujiwara, M.; Kajihara, K.; Erabi, T. Bull. Chem. Soc. Jpn. 1991, 64, 1782.
14. (c) Suzuki, H.; Ikegami, T.; Azuma, N. J. Chem. Soc., Perkin Trans. 1 1997, 1609. Thus, in compounds 3ba and 3bb, the ortno-methoxyl groups may also afford thermodynamic stabilization to the Bi=N bond.
15. -1, Cristau, H. J.; Manginot, E.; Torreilles, E. Synthesis 1991, 382.
16. w = 3.4%, GOF = 1.11. For further details, see Supporting Information.
17. (a) Clegg, W.; Compton, N. A.; Errington, R. J.; Norman, N. C.; Wishart, N. Polyhedron 1989, 8, 1579.
18. (b) Clegg, W. Compton, N. A.; Errington, R. J.; Fisher, G. A.; Green, M. E.; Hockless, D. C. R.; Norman, N. C. Inorg. Chem. 1991, 30, 4680.
19. (c) Wirringra, U.; Roesky, H. W.; Noltemeyer, M.; Schmidt, H.-G. Inorg. Chem. 1994, 33, 4607.
20. (d) Edwards, A. J.; Beswick, M. A.; Galsworthy, J. R.; Paver, M. A.; Raithby, P. R.; Rennie, M.-A.; Russell, C. A.; Verhorevoort, K. L.; Wright, D. S. Inorg. Chim. Acta 1996, 248, 9.
21. e) Burford, N.; Macdonald, C. L. B.; Robertson, K. N.; Cameron, T. S. Inorg. Chem. 1996, 35, 4013.
22. 2 to be 0.927 from ab initio calculations (MP2/DZ-d level). Koketsu, J.; Ninomiya, Y.; Suzuki, Y.; Koga, N. Inorg. Chem. 1997, 36, 694.
23. sp2=O bond lengths are 1.36 and 1.20 Å, respectively. See: March, J. Advanced Organic Chemistry, 4th ed.; Wiley: New York, 1992; Table 1.5, p 21.
24. All products were identified by comparison with the authentic specimens. Amide 2a was an accompanying byproduct in the thermal decomposition, oxidation, and acidolysis. See Supporting Information.
25. At present, we assume that 3aa decomposes to generate a nitrene or nitrenoid species, which would abstract hydrogens from the solvent or the aryl ligands.
26. (a) Staudinger, H.; Hauser, E. Helv. Chim. Acta 1921, 4, 861.
27. (b) Horner, L.; Gross, A. Justus Liebigs Ann. Chem. 1955, 591, 117.
28. This compound was obtained from the KOt-Bu-promoted reaction of 1a and trifluoromethanesulfonamide. Matano, Y.; Nomura, H.; Suzuki, H. Unpublished results.
29. For reviews on the ligand coupling of hypervalent compounds, see: (a) Barton, D. H. R.; Finet, J.-P. Pure Appl. Chem. 1987, 59, 937.
30. (b) Finet, J.-P. Chem. Rev. 1989, 89, 1487.
31. (c) Oae, S. Pure Appl. Chem. 1996, 68, 805, and references therein.