sym-[5.5.5]Heterocyclophanes: Structurally well-defined, mixed π/heteroatom-donor macrobicyclic cages

Journal of the Chemical Society - Perkin Transactions 1

Volumn , Issue 20, 1998, Pages 3371-3376

  Hansen, Jens ^a   Blake, Alexander J ^a   Li, Wan Sheung ^a   Mascal, Mark ^a  

^a UNIVERSITY OF NOTTINGHAM   (United Kingdom)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 33748491061     PISSN: 0300922X     EISSN: None     Source Type: Journal    
DOI: 10.1039/a805646c     Document Type: Article

References (27)

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2. J. Dale, Angew. Chem., Int. Ed. Engl., 1966, 5, 1000.
3. This naturally assumes that the linking chains provide for a sufficient separation between the two π-systems. For methylene groups, the first odd number to satisfy this condition is 5.
4. A literature search for [n.n]paracyclophanes and sym-[n.n.n.]cyclophanes from n = 5 to 12 was performed where the atoms could be any non-metal with any substituent, but with the condition that the bridging atoms participate in single bonds only. This query produced an equal number of [odd.odd] and [even.even] paracyclophanes (92 each), and 19 [odd.odd.odd] versus 16 [even.even.even]sym-[n.n.n]cyclophanes.
5. 2-]-bridged- (K. E. Krakowiak and J. S. Bradshaw, J. Heterocycl. Chem., 1996, 33, 1)
6. 2N(R)-]-bridged- (P. L. Anelli, L. Lunazzi, F. Montanari and S. Quici, J. Org. Chem., 1984, 49, 4197) sym[7.7.7]cyclophanes.
7. Cambridge Structural Database Ver. 5.15 (181309 structures, April 1998 release): F. H. Allen and O. Kennard, Chemical Design 'Automation News, 1993, 8, 31. Note here that no examples sym-[n.n.n]cyclophanes with saturated bridges occur in the Database.
8. R. Benn, N. E., Blank, M. W. Haenel, J. Klein, A. R. Koray, K. Weidenhammer and M. L. Ziegler, Angew. Chem., Int. Ed. Engl., 1980, 19, 44.
9. This is shown by molecular mechanics simulations (MACRO-MODEL ver. 4.0 with the MM3 force field: F. Mohamadi, N. G. J. Richards, W. C. Guida, R. Liskamp, M. Lipton, C. Caufield, G. Chang, T. Hendrickson and W. C. Still, J. Comput. Chem., 1990, 11, 440). The next conformationally stable homologue, the [7.7.7] cyclophane, has an Ar ⋯ Ar separation some 3 Å greater than the [5.5.5] system.
10. 2 complexes in the solid state, M. Mascal, submitted for publication.
11. M. Mascal, J.-L. Kerdelhué, A. S. Batsanov and M. J. Begley, J. Chem. Soc., Perkin Trans. 1, 1996, 1141.
12. Preliminary communication: M. Mascal, J. Hansen, A. J. Blake and W.-S. Li, Chem. Commun., 1998, 355.
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18. Review: R. H. Crabtree, Angew. Chem., Int. Ed. Engl., 1993, 32, 789.
19. Cambridge Structural Database refcodes: CELKEJ(01), ENCCBP10, GALTUI, JOBVUR, KAHBIE(10), LEDTIX: The conditions for eta complexation were met when a (generalized) metal was closer to a single carbon atom of an arene ring than to the midpoint of the bond connecting that carbon to the adjacent ring carbon (eta-1), or when the metal was closer to the midpoint of an arene carbon-carbon bond than to either of the carbon atoms between which the bond is made (eta-2). The metal to carbon (or metal to bond midpoint) distance was limited to 3.0 A and the metal-carbon (or midpoint)-aryl centroid angle, was limited to the range 80-100°.
20. c/δv)] was used: R. K. Harris, Nuclear Magnetic Resonance Spectroscopy - A Physicochemical Approach, Pitman, London, 1983.
21. Eta-1 complexation to silver has been discussed (K. Shelly, D. C. Finster, Y. J. Lee, R. Scheidt and C. A. Reed, J. Am. Chem. Soc., 1985, 107, 5955),
22. 3-silver-deltaphane (1,2,4,5-[2.2.2.2.2.2]cyclophane) complex (H. C. Kang, A. W. Hanson, B. Eaton and V. Boekelheide, J. Am. Chem. Soc., 1985, 107, 1979).
23. W. P. Cochrane, P. L. Paulson and T. S. Stevens, J. Chem. Soc. (C), 1968, 630.
24. G. M. Sheldrick, SHELXS-96. Acta Crystallogr., Sect. A, 1990, 46, 467.
25. G. M. Sheldrick, SHELXL-96. University of Göttingen, Germany, 1996.
26. G. M. Sheldrick, SHELXTL/PC ver. 5.03, Siemens Analytical Instrumentation Inc., Madison, WI, USA, 1994.
27. The United Kingdom Chemical Database Service: D. A. Fletcher, R. F. McMeeking and D. Parkin, J. Chem. Inf. Comput. Sci., 1996, 36, 746.