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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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|
|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|
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