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[n]peristylanes and [n]oxa[n]peristylanes (n = 3-6): A theoretical study

Sharma, Pankaz K and Jemmis, Eluvathingal D and Vidya, Ramdas and Mehta, Goverdhan (1999) [n]peristylanes and [n]oxa[n]peristylanes (n = 3-6): A theoretical study. In: Perkin Transactions 2 (2). 257-262 .

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Theoretical studies at the HF and Becke3LYP levels using 6-31G* basis sets were carried out on a series of [n]peristylanes and [n]oxa[n]peristylanes (n = 3-6) to understand their structure and energetics. The structures of the [3]- and [4]peristylanes (1, 2) and their era-derivatives (5, 6) were calculated to have the anticipated high symmetry, C-nv. In contrast, a C-s structure (9) at HF/6-31G* and another (25) at the Becke3LYP/6-31G* level were calculated for the [5]oxa[5]peristylane. The energy difference between them is extremely small even though there are major differences in the structures indicating every soft potential energy surface: On the other hand, the potential energy surface of [6]oxa[6]peristylane is not as soft. Similar structures were also calculated for the top rings. Calculations on the seco-compounds 11-14 and 15-19 (Table 4) indicate that there is no unusual strain involved in the formation of 27 from 19. The Li+ interaction energies of the [n]oxa[n]peristylanes are 61.7 (n = 3), 72.8 (n = 4), 84.2 (n = 5) and 91.7 (n = 6) kcal mol(-1) at the Becke3LYP/6-3IG* level. Dramatic differences between the C-C bond lengths obtained from the solid state X-ray diffraction studies and those from the calculations for the [n]oxa[n]peristylanes were also observed.

Item Type: Journal Article
Publication: Perkin Transactions 2
Publisher: Royal Society of Chemistry
Additional Information: Copyright of this article belongs to Royal Society of Chemistry.
Department/Centre: Division of Chemical Sciences > Organic Chemistry
Date Deposited: 29 Jun 2011 05:52
Last Modified: 29 Jun 2011 05:52
URI: http://eprints.iisc.ac.in/id/eprint/38699

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