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The Friedel–Crafts acetylation (Ac2O/AlCl3) reaction of azinylferrocenes occurs regioselectively at position 1′. Acetylated derivatives upon reaction with Ph3P=CH2 give the corresponding 1-azinyl-1′-isopropenylferrocenes.

In the present review comparative data concerning various synthetic approaches and methodologies used in the series of ferrocene and cymantrene derivatives to create various materials, namely, catalytic systems, sensory and other molecular devices, polymers as well as physiologically active substances, for the period from 2000 till 2016 are given. Aspects of practical application of the above compounds are also considered.

A highly selective coupling of azines with aromatic nucleophiles (SN H-reactions) in the presence of a heterogeneous oxidation system O2/CdS/TiO2 upon exposure to daylight was accomplished.

Novel non-symmetric tridentate N,N,O-ligand was obtained by direct substitution of hydrogen in 3-(2-pyridyl)-6-phenyl-1,2,4-triazine. Three binuclear cobalt(II), copper(II) and zinc(II) carboxylate complexes of 3-(2-pyridyl)-5-(2-hydroxynaphthalen-1-yl)-6-phenyl-1,2,4-triazine anion (HL1), [M2(Piv)2(L1)2] (M = Co, Cu, Zn; Piv = Me3CCO2-), were synthesized and characterized by elemental analysis and IR spectroscopy. The complexes structures were determined by single crystal X-ray diffraction analysis. The magnetic property studies indicate that cobalt(II) complex exhibits weak ferromagnetic coupling (J = 1.2(1) cm−1) between two high-spin Co(II) ions linked by double μ-O phenoxo bridges. According to magnetic property studies as well as X- and Q-band EPR spectra for copper(II) complex, the specific structure of the Cu2O2 fragment leads to the predominance of dipole–dipole interactions and weak antiferromagnetic coupling (J = -3.64(3) cm−1).

The facile C–C coupling reaction of activated forms of azaaromatics (azine-N-oxides) with cymantrenyl lithium, as a nucleophile, has first been carried out. It has been established that aromatization of intermediate adducts can be realized through either oxidative or eliminative pathways, depending on the structure of the starting azine N-oxide. In particular, the dihydroazinyl intermediates, bearing the additional N(4)-atom relative to the N-oxide group, proved to undergo aromatization through the eliminative pathway. The X-ray studies of 3,6-diphenyl-1,2,4-triazine-5-yl-cymantrene have revealed that it is crystallized in both orthorhombic and monoclinic forms. © 2018 Elsevier B.V.

Novel complexes of 1,2-P,N-bidentate ferrocenyl ligands with AgOAc or with [RuCl2(PPh3)3] as catalysts have been studied in asymmetric synthesis. The catalytic activity of these systems have been studied in [3+2]-cycloaddition of azomethine ylides with olefins and the asymmetric transfer hydrogenation of ketones.