Controlling the reactive state through cation binding: photochemistry of enones within zeolites

Uppili, Sundararajan and Takagi, Shinsuke and Sunoj, RB and Lakshminarasimhan, P and Chandrasekhar, J and Ramamurthy, V (2001) Controlling the reactive state through cation binding: photochemistry of enones within zeolites. In: Tetrahedron Letters, 42 (11). pp. 2079-2083.

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Abstract

The nature of the lowest triplet state of enones is altered by the cations present within Y zeolites. Alkali metal ions, such as $Li^+$, are predicted to interact with the carbonyl unit of enones in a collinear fashion and significantly lower both the p-type n and \pi -2 orbitals. Excited state energies, estimated at the $CIS(D)/6-31+G^*$ level, show that the lowest triplet is $n-\pi^*$ in character for the enones, but switch to \pi–$\pi^*$on coordination with $Li^+$. Observed product distribution within zeolite is consistent with thistheoretical prediction.

Item Type:	Journal Article
Publication:	Tetrahedron Letters
Publisher:	Elsevier Science
Additional Information:	Copyright of this article belongs to Elsevier Science
Department/Centre:	Division of Chemical Sciences > Organic Chemistry
Date Deposited:	26 Dec 2008 10:31
Last Modified:	19 Sep 2010 04:53
URI:	http://eprints.iisc.ac.in/id/eprint/16690

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