Cobalt-Mediated Synthesis of Angular [4]Phenylene: Structural Characterization of a Metallacyclopentadiene(Alkyne) Intermediate and Its Thermal and Photochemical Conversion

Organic Letters

Volumn 4, Issue 12, 2002, Pages 2075-2078

  Dosa, Peter I ^a   Whitener, Glenn D ^a   Vollhardt, K Peter C ^a   Bond, Andrew D ^b   Teat, Simon J ^c  

^a UNIVERSITY OF CALIFORNIA   (United States)

^b UNIVERSITY OF CAMBRIDGE   (United Kingdom)

^c DARESBURY LABORATORY   (United Kingdom)

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ARTICLE;

EID: 0005312376     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol025956o     Document Type: Article

References (23)

1. Vollhardt, K. P. C.; Mohler, D. L. In Advances in Strain in Organic Chemistry; Halton, B., Ed.; JAI: London, 1996; pp 121-160.
2. (a) For biphenylene, see: Fawcett, J. K.; Trotter, J. Acta Crystallogr. 1966, 20, 87.
3. (b) For angular [3]phenylene, see: Diercks, R.; Vollhardt, K. P. C. Angew. Chem., Int. Ed. Engl. 1986, 25, 266.
4. (c) For linear [3]phenylene, see: Schleifenbaum, A.; Feeder, N.; Vollhardt, K. P. C. Tetrahedron Lett. 2001, 42, 7329.
5. (d) For triangular [4]phenylene, see: Holmes, D.; Kumaraswamy, S.; Matzger, A. J.; Vollhardt, K. P. C. Chem. Eur. J. 1999, 5, 3399.
6. For a recent theoretical study of this mechanism as it pertains to CpCo, see: Hardesty, J. H.; Koerner, J. B.; Albright, T. A.; Lee, G.-Y. J. Am. Chem. Soc. 1999, 121, 6055.
7. See: Diercks, R.; Eaton, B. E.; Jalisatgi, S.; Matzger, A. J.; Radde, R. H.; Vollhardt, K. P. C. J. Am. Chem. Soc. 1998, 120, 8247 and references therein.
8. Schmidt-Radde, R. H.; Vollhardt, K. P. C. J. Am. Chem. Soc. 1992, 114, 9713.
9. Dosa, P. I.; Schleifenbaum, A.; Vollhardt, K. P. C. Org. Lett. 2001, 3, 1017.
10. NICS(1) values from: Schulman, J. M.; Disch, R. L.; Jiao, H.; Schleyer, P. v. R. J. Phys. Chem. A 1998, 102, 8051 . For additional theoretical studies of the phenylenes, see: Schulman, J. M.; Disch, R. L. J. Am. Chem. Soc. 1996, 118, 8470; J. Phys. Chem. A 1997, 101, 5596 and references therein.
11. NICS(1) values from: Schulman, J. M.; Disch, R. L.; Jiao, H.; Schleyer, P. v. R. J. Phys. Chem. A 1998, 102, 8051 . For additional theoretical studies of the phenylenes, see: Schulman, J. M.; Disch, R. L. J. Am. Chem. Soc. 1996, 118, 8470; J. Phys. Chem. A 1997, 101, 5596 and references therein.
12. NICS(1) values from: Schulman, J. M.; Disch, R. L.; Jiao, H.; Schleyer, P. v. R. J. Phys. Chem. A 1998, 102, 8051 . For additional theoretical studies of the phenylenes, see: Schulman, J. M.; Disch, R. L. J. Am. Chem. Soc. 1996, 118, 8470; J. Phys. Chem. A 1997, 101, 5596 and references therein.
13. The structure is in excellent agreement with calculations at the B3LYP/6-31G* level: Professor P. von Ragué Schleyer and Dr. H. Jiao, private communication. The maximum deviation of the calculated from the experimental bond lengths is 0.025 Å, and the average deviation is 0.012 Å.
14. The formula [Σ single-bond lengths - Σ double-bond lengths]/3 provides a quantitative measure of bond alternation in each ring. This number was normalized using the exocyclic diene portion of 3,4-dimethylenecyclobutene (1.497, 1.338 Å) as a 100% standard. See: Beckhaus, H.-D.; Faust, R.; Matzger, A. J.; Mohler, D. L.; Rogers, D. W.; Rüchardt, C.; Sawhney, A. K.; Verevkin, S. P.; Vollhardt, K. P. C.; Wolff, S. J. Am. Chem. Soc. 2000, 122, 7819 and references therein.
15. xCpCo(CO)(alkyne) systems: Benisch, C.; Chávez, J.; Gleiter, R.; Nuber, B.; Irngartinger, H.; Oeser, T.; Pritzkow, H.; Rominger, F. Eur. J. Inorg. Chem. 1998, 629, 9.
16. A search of the Cambridge Structural Database failed to uncover a structurally characterized Co(III)-alkyne complex. For examples of Co(I) complexes with shorter Co-alkyne bonds, see: (a) ref 10. (b) Foerstner, J.; Kettenbach, R.; Goddard, R.; Butenschön, H. Chem. Ber. 1996, 129, 319. (c) Okuda, J.; Zimmermann, K. H.; Herdtweck, E. Angew. Chem., Int. Ed. Engl. 1991, 30, 430. For a discussion of how bond distances may vary with an oxidation state, see: Frenking, G.; Fröhlich, N. Chem. Rev. 2000, 100, 717.
17. A search of the Cambridge Structural Database failed to uncover a structurally characterized Co(III)-alkyne complex. For examples of Co(I) complexes with shorter Co-alkyne bonds, see: (a) ref 10. (b) Foerstner, J.; Kettenbach, R.; Goddard, R.; Butenschön, H. Chem. Ber. 1996, 129, 319. (c) Okuda, J.; Zimmermann, K. H.; Herdtweck, E. Angew. Chem., Int. Ed. Engl. 1991, 30, 430. For a discussion of how bond distances may vary with an oxidation state, see: Frenking, G.; Fröhlich, N. Chem. Rev. 2000, 100, 717.
18. A search of the Cambridge Structural Database failed to uncover a structurally characterized Co(III)-alkyne complex. For examples of Co(I) complexes with shorter Co-alkyne bonds, see: (a) ref 10. (b) Foerstner, J.; Kettenbach, R.; Goddard, R.; Butenschön, H. Chem. Ber. 1996, 129, 319. (c) Okuda, J.; Zimmermann, K. H.; Herdtweck, E. Angew. Chem., Int. Ed. Engl. 1991, 30, 430. For a discussion of how bond distances may vary with an oxidation state, see: Frenking, G.; Fröhlich, N. Chem. Rev. 2000, 100, 717.
19. A search of the Cambridge Structural Database failed to uncover a structurally characterized Co(III)-alkyne complex. For examples of Co(I) complexes with shorter Co-alkyne bonds, see: (a) ref 10. (b) Foerstner, J.; Kettenbach, R.; Goddard, R.; Butenschön, H. Chem. Ber. 1996, 129, 319. (c) Okuda, J.; Zimmermann, K. H.; Herdtweck, E. Angew. Chem., Int. Ed. Engl. 1991, 30, 430. For a discussion of how bond distances may vary with an oxidation state, see: Frenking, G.; Fröhlich, N. Chem. Rev. 2000, 100, 717.
20. (a) Gleiter, R.; Merger, R. In Modern Acetylene Chemistry; Stang, P. J., Diederich, F., Eds.; VCH: Weinheim, Germany, 1995; pp 285-319.
21. (b) De Graaff, R. A. G.; Gorter, S.; Romers, C.; Wong, H. N. C.; Sondheimer, F. J. Chem. Soc., Perkin Trans. 1 1981, 478.
22. For a tabulation, see: Benisch, C.; Gleiter, R.; Staeb, T. H.; Nuber, B.; Oeser, T.; Pritzkow, H.; Rominger, F. J. Organomet. Chem. 2002, 641, 102.
23. Rausch, M. D.; Tokas, E. F.; Gardner, S. A.; Clearfield, A.; Chinn, J. W., Jr.; Bernal, I. J. Organomet. Chem. 1981, 212, 247.