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Effect of meta Electron-donating Groups on the Electronic Structure of Substituted Phenyl Nitrenium Ions

Winter, A. H.; Falvey, D. E.; Cramer, C. J.
J. Am. Chem. Soc. 2004, 126, 9661.

Density functional theory (UB3LYP/6-31G(d,p)) was used to determine substituent effects on the singlet-triplet state energy gap for 21 meta-substituted phenylnitrenium ions. It was found that strongly electron-donating substituents stabilize the triplet state relative to the singlet state. With sufficiently strong meta electron donors (e.g. m,m'-diaminophenylnitrenium ion) the triplet is predicted to be the ground state. Analysis of equilibrium geometries, Kohn-Sham orbital distributions, and Mulliken spin densities for the triplet states of this series of nitrenium ions leads to the conclusion that there are two spatially distinct types of low-energy triplet states. Simple arylnitrenium ions such as phenylnitrenium ions as well as those having electron withdrawing or weakly donating metasubstituents have lowest-energy triplet states that are n,p* in nature. That is, one singly occupied molecular orbital is orthogonal to the plane of the phenyl ring and one is coplanar. These n,p* triplets are generally characterized by large ArNH bond angles (ca. 130-132 deg) and an NH bond that is perpendicular to the plane of the phenyl ring. In contrast, meta-donor arylnitrenium ions have a lowest-energy triplet state best described as p,p*. That is, both singly occupied molecular orbitals are orthogonal to the aromatic ring. Such p,p* states are characterized by NH bonds that are coplanar with the phenyl ring and have ArNH bond angles that are more acute (ca. 110-111 deg). These triplet nitrenium ions have electronic structures analogous to those of meta-benzoquinodimethane derivatives.

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