The phototautomerization mechanism of a model nitro enamine (NEA) chromophore (incorporated in the structure of a highly photolabile pesticide, tetrahydro-2-(nitromethylene)-2H-1,3-thiazine) has been studied using complete active space self-consistent field reaction path computations. The optically accessible 1ππ* excited state of NEA involves separation of charge and correlates diabatically with the ground state of the tautomerized acinitro imine (ANI) form. For optimum photostabilization, the 1ππ* state of NEA should be S1: in this case, the tautomer would be efficiently formed via a diabatic intramolecular proton-transfer pathway passing through an S1/S0 conical intersection, followed by a facile thermal back proton-transfer reaction. However, in NEA itself the lowest excited states correspond to nitro group 1nπ* states, and there are additional surface crossings that provide a mechanism for populating the 1nπ* manifold. The above results indicate that the high photolability observed for the pesticide [Kleier, D.; Holden, I.; Casida, J. E.; Ruzo, L. O. J. Agric. Food Chem. 1985, 33, 998-1000] has to be ascribed to photochemistry originating on the 1n;π* manifold of states, populated indirectly from the 1ππ* state. © 2007 American Chemical Society.

Migani, A., Bearpark, M.J., Olivucci, M., Robb, M.A. (2007). Photostability versus Photodegradation in the Excited-State Intramolecular Proton Transfer of Nitro Enamines:  Competing Reaction Paths and Conical Intersections. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 129(12), 3703-3713 [10.1021/ja066592o].

Photostability versus Photodegradation in the Excited-State Intramolecular Proton Transfer of Nitro Enamines:  Competing Reaction Paths and Conical Intersections

Olivucci, Massimo;
2007-01-01

Abstract

The phototautomerization mechanism of a model nitro enamine (NEA) chromophore (incorporated in the structure of a highly photolabile pesticide, tetrahydro-2-(nitromethylene)-2H-1,3-thiazine) has been studied using complete active space self-consistent field reaction path computations. The optically accessible 1ππ* excited state of NEA involves separation of charge and correlates diabatically with the ground state of the tautomerized acinitro imine (ANI) form. For optimum photostabilization, the 1ππ* state of NEA should be S1: in this case, the tautomer would be efficiently formed via a diabatic intramolecular proton-transfer pathway passing through an S1/S0 conical intersection, followed by a facile thermal back proton-transfer reaction. However, in NEA itself the lowest excited states correspond to nitro group 1nπ* states, and there are additional surface crossings that provide a mechanism for populating the 1nπ* manifold. The above results indicate that the high photolability observed for the pesticide [Kleier, D.; Holden, I.; Casida, J. E.; Ruzo, L. O. J. Agric. Food Chem. 1985, 33, 998-1000] has to be ascribed to photochemistry originating on the 1n;π* manifold of states, populated indirectly from the 1ππ* state. © 2007 American Chemical Society.
2007
Migani, A., Bearpark, M.J., Olivucci, M., Robb, M.A. (2007). Photostability versus Photodegradation in the Excited-State Intramolecular Proton Transfer of Nitro Enamines:  Competing Reaction Paths and Conical Intersections. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 129(12), 3703-3713 [10.1021/ja066592o].
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11365/31749
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