Computational analysis of the dinitramine and chlorine derivatives of benzene and s-tetrazine

doi:10.1016/0166-1280(92)85106-U

Journal of Molecular Structure: THEOCHEM

Volume 262, October 1992, Pages 155-170

https://doi.org/10.1016/0166-1280(92)85106-U Get rights and content

Abstract

Optimized HF/3-21G^∗ geometries were computed for s-tetrazine (I) and for the dinitramine and chlorine derivatives of I and of benzene. These structures were used to calculate the electrostatic potentials and average local ionization energies of these molecules. HF/3-21G^∗ and MP2/6-31G^∗ geometries were also computed for pentazine (VI), which is as yet unknown, and shown to correspond to energy minima. The electrostatic potential on the surface of I is strongly negative above the electron-attracting ring nitrogen atoms and positive above the ring and the hydrogen atoms, fully consistent with the structures of complexes that s-tetrazine is known to form with other molecules. Previously developed relationships were used to estimate the Hammett constants σ_m and σ_p of the dinitramine group, N(NO₂)₂, and the pK_a values of s-tetrazine, its dinitramine and chlorine derivatives, and pentazine. N(NO₂)₂ is found to be strongly electron withdrawing through induction and more weakly donating through resonance. In the s-tetrazine derivatives, the electron attracting power of the ring nitrogen atoms significantly increases the extents of conjugation of the N(NO₂)₂ and Cl, both resonance donors. However, the dominant effect of these substituents upon the ring is inductive deactivation toward electrophiles.

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Computational analysis of the dinitramine and chlorine derivatives of benzene and s-tetrazine

Abstract

J. Mol. Struct. (Theochem)

J. Mol. Struct. (Theochem)

J. Mol. Spectrosc.

J. Org. Chem.

J. Am. Chem. Soc.

J. Comput. Chem.

J. Am. Chem. Soc.

Helv. Chim. Acta

J. Am. Chem. Soc.

J. Am. Chem. Soc.

J. Phys. Chem.

J. Phys. Chem.

J. Mol. Struct. (Theochem)

J. Org. Chem.

J. Mol. Struct. (Theochem)

J. Phys. Chem.

J. Phys. Chem.

J. Phys. Chem.

Struct. Chem.

J. Phys. Chem.

J. Phys. Chem.

J. Phys. Chem.

Struct. Chem.

Kinet. Katal.

Zh. Org. Khim.

Zh. Org. Khim.