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• W1996091796 abstract "Structures of Sterically Overcrowded and Charge-Perturbed Molecules, 38[1]. — The Different Conformations of N-Trimethylsilyl-Substituted p-Phenylenediamine Derivatives: Investigation of Single Crystals and in the Gas Phase The ESR-proven generation of a Wurster's Blue radical anion by one-electron reduction of N,N,N′,N′-tetrakis(trimethylsilyl)-p-phenylenediamine is rationalized by a posterior singlecrystal structure determination of the neutral molecule, which demonstrates inter alia that the bulky [(H3C)3Si]2N substituents are twisted out of the benzene plane by 83°. In contrast, the skeleton of the sterically congested N,N′-bis(trimethylsilyl)-p-phenylenediamine remains almost planar and, accordingly, allows nN/π interaction between the p-type nitrogen electron pairs of the also flattened [(H3C)3Si]HN groups and the benzene π system. These conformational differences are reflected in the gas-phase photoelectron spectra, in which nN/π ionisation bands are split by less than 1 eV or more than 3 eV, respectively. The evidence for analogous structures of the two organosilicon p-phenylenediamine derivatives in solution is confirmed by geometry-optimized AM1 calculations, which readily explain the surprising insertion of an extra electron into an already electron-rich molecule." @default.
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• W1996091796 date "1994-01-01" @default.
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• W1996091796 title "Die verschiedenartigen Konformationen <i>N</i> ‐Trimethylsilyl‐substituierter <i>p</i> ‐Phenylendiamin‐Derivate: Untersuchungen an Einkristallen sowie in der Gasphase" @default.
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• W1996091796 doi "https://doi.org/10.1002/cber.19941270109" @default.
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