The reaction product of Cp*Ru(CH3CN)3+ OSO2CF3− with salicylaldehyde yielded (1) which reacted with a series of aniline derivatives to produce air-stable solids. These products were characterized by 1H and 13C NMR spectrometry and UV–Vis spectroscopy. Solvatochromism studies of these products revealed that the p-NH2 and p-N(CH3)2 derivatives exhibit relatively large values of molecular hyperpolarizability and have the potential to exhibit nonlinear optical properties. These derivatives were further studied by electrochemical investigations.

Cp* Ru(η6-C6H5CHO)+OSO2CF3− (1) (Cp* = C5Me5) reacts with substituted anilines forming ruthenium Schiff base complexes containing an η6-coordinated Cp* Ru+ group. The 2:1 reaction of 1 with 1,4-phenylenediamine yielded only the monocondensation product, whereas the 2:1 reaction of 1 with 1,4-xylylenediamine yielded the dicondensation product.

Ten novel [Cp∗Ru(η6-monosubstituted naphthalene)+O3SCF3− complexes were synthesized and characterized by 1H, 13C and 1H{1H}-COSY NMR spectrometry. All complexes containing electron-withdrawing substituents formed products with Cp∗Ru+ moeity coordinated on the unsubstituted ring. In [Cp∗Ru(η6-1-naphthalamine)]+O3SCF3−, ruthenium is coordinated on the substituted ring due to the electron-donating properties of the NH2 group. However, the methoxy and N,N-dimethylamine derivatives, despite the electron-donating properties of the substituents, coordinate the ruthenium atom on the unsubstituted ring due to steric hindrance around the substituted ring. Methylnaphthalene and hydroxynaphthalene products were formed as mixtures of coordination isomers.

An investigation of the scope and mechanism of a new synthesis of cyclopentenes from 3,6-dihydro-2H-thiopyrans is described. Alkyl halides substituted with an electron-withdrawing group in the alpha-position were reacted with sodium thiosulfate, yielding the corresponding Bunte salts, which could be transformed to reactive thiocarbonyl compounds by elimination of the elements of bisulfite with mild base treatment. In situ trapping by 1,3-dienes afforded in good yields a variety of 3,6-dihydro-2H-thiopyrans substituted with electron-withdrawing groups at the 2-position. Exposure of these cycloadducts to strong base at low temperature effected a novel ring contraction, affording 2-(methylthio)-3-cyclopentenes after quenching with methyl iodide. The level of diastereoselectivity exhibited during the generation of these cyclopentenes was found to be dependent on the nature of the electron-withdrawing group at the 2-position of the dihydrothiopyran as well as the substitution pattern originally present in the diene component. In some cases, reducing the temperature during the ring contraction resulted in the isolation of good yields of vinyl cyclopropanes of high isomeric purity. With one substrate, highly diastereoselective rearrangement of a vinyl cyclopropane to a cyclopentene was unambiguously demonstrated, suggesting that this might be a key feature of the overall ring contraction mechanism.