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The structures of seven di- or tetrasubstituted p-benzoquinone derivatives O=C(XC=CH )2C=O and O=C(XC=CX)2C=O with substituents X = -OCH3, -N(CH2)5, - N(CH2CH2)2O, -Cl, -CN and -⊕N(HC=CH)2C-N(CH3)2 are presented and discussed in comparison with published ones substituted by X = -Si(CH3)3, -C6H5, -N(CH3)2, -⊕N(HC=CH)2CN(CH3)2, -O⊖ , and - NO2. Based on the introduction, in which halfwave-reduction potentials, geometry-optimized quantum-chemical calculations on substituent perturbation and known structural data of p-benzoquinone derivatives are used to characterize their molecular ground states. The structural changes indicate how substituent perturbations might be rationalized. Of the categories defined - imperturbed, donor, donor/acceptor and acceptor perturbed - the donorsubstituted p-benzoquinones do exhibit the largest differences, often called cyanine distorsion. In very satisfactory agreement with extensive semiempirical calculations, all effects determined experimentally are discussed in terms of varying charge distribution. With respect to the biochemical importance of p-benzoquinone derivatives, this first structural summary points out important facets.
Das Reduktionsverhalten von Pentacarbonylpyridin-Komplexen des Chroms, Molybdäns und Wolframs
(1984)
The reduction of group VIB metal pentacarbonyl complexes and of iodomethylates of 4- trimethylsilyl-, 4-acetyl- and 4-cyanopyridine has been investigated. Informations on the dissociation of the complexes and on the potential and reversibility of the one-electron reduction were obtained by cyclic voltammetry in DMF, whereas electron spin resonance (ESR) studies of the primary reduction products in the 4-acetylpyridine series revealed the distribution of the unpaired electron. The results suggest that the lowest unoccupied molecular orbital (LUMO) is a ligand centered π*-orbital in the 4-acetyl- and 4-cyanopyridine complexes, thus confirming assignments from photochemistry. The results allow an assessment of both N-coordination and substituent effects at the heterocyclic ligand.
The He I photoelectron spectra of the series RnP(CN)3-n (R = Me, CF3; n = 0, 1, 2, 3) and of Me2ECN (E = N, P, As) are interpreted. The PE assignments are based on the comparison with the PE data of analogous halogeno and hydrogen derivatives as well as related cyano compounds and on simple MO considerations (composite molecule-approach). Hyperconjugative and inductive effects of the substituents CN, Me, F, Cl, and especially CF3 are assessed. The various effects of changing substituents or central atoms within the series are used to confirm the interpretation. The differing electronic structures of halogeno and cyano (pseudohalogeno) compounds are discussed on the basis of their PE spectra.