S. N. Bizyaev

Co(III) complexes with optically active bis(menthane), pinano-para-menthane, carano-para-menthane, and bis(carane) propylenediaminodioximes

Novel optical ligands bis(menthane) (H2L1), pinano-para-menthane (H2L2), and carano-para-menthane (H2L3) propylenediaminodioximes are obtained. Diamagentic Co(III) complexes of the composition Co(HL1)Cl2 (I), Co(HL2)Cl2 (II), Co(HL3)Cl2 (III), and Co(HL4)Cl2 · H2O(IV) are synthesized by reactions of CoCl2 with H2L1, H2L2, H2L3 and bis(carane) propylenediaminodioxime (H2L4) in ethanol in air. The crystal and molecular structures of compound I is determined by X-ray diffraction analysis. The crystals are monoclinic with the unit cell parameters a = 7.8385(3) Å, b = 11.4074(6) Å, c = 14.9509(6) Å, β = 104.278(2)°, V = 1295.57(10) Å3, Z = 2, ρ(calcd) = 1.367 g/cm3, F(000) = 564, M = 533.41, space group P21. The crystal structure of complex I consists of individual mononuclear molecules. The Co3+ ion coordinates four N atoms of tetradentate cycle-forming anionic ligand and two Cl atoms. The coordination polyhedron of Cl2N4 is a distorted octahedron. The 13C and 1H NMR spectra of the complexes synthesized confirm coordination of four N atoms of a ligand.

Binuclear Pd(II) complexes with chiral ethylenediaminodioxime (H2L) and bis-α-thiooxime (H2L1), the derivative of monoterpenoid(+)-3-carene. Crystal structures of [Pd2(H2L)Cl4] and [Pd2(H2L1)Cl4] · 3CDCl3

Diamagnetic Pd(II) complexes with the chiral ethylenediaminodioxime (H 2 L) and bis-α-thiooxime (H2L1), the derivatives of monoterpenoid (+)-3-carene, of the composition Pd2(H2L)Cl4(I), Pd2(H2L1)Cl4 (II), and the solvate Pd2(H2L1)Cl4·3DCl3 (III) were synthesized. The crystal structures of complex I and solvate III were determined from X-ray diffraction data. The structures consist of acentric binuclear molecules with the coordination cores PdN2Cl2 (in I) and PdNSCl2 (in III) in the form of the distorted squares. In complex I, each Pd atom coordinates two N atoms of the tetradentate bridge-cyclic ligand H2L and two Cl atoms; in compound III, one N and one S atom of the tetradentate bridge-cyclic ligand H2L1, and 2 Cl atoms. The CDCl3 molecules in compound III lie in the cavities formed by the molecules of complex II. In both structures, the PdCl2 fragments are in the trans-positions. The 1H NMR spectra indicate that the structures of complexes I, II in solutions are similar to the structures of compounds I, III in the solid state.

Complexes [Cu(H2L)](NO3)2 and [Cu(H2L)Cl]2[CuCl2]Cl · 0.5H2O (H2L is chiral bis(menthane) propylenediaminodioxime): Synthesis and structure

The synthesis of the [Cu(H2L)](NO3)2 complex (I) and of a mixed-valent complex [Cu(H2L)Cl]2[CuCl2]Cl·0.5H2O (II), where L is chiral bis(menthane) propylenediaminodioxime. According to the data of single-crystal X-ray diffraction analysis, compounds I and II have ionic structures. In complex cations, the Cu2+ ion coordinates four N atoms of tetradentate chelate ligand, namely, the H2L molecule. The coordination surrounding of the Cu atom in I is a distorted square CuN4, while in II, it is a distorted square pyramid CuN4Cl. The complex anion [CuCl2]− in II has linear structure. The mutual arrangement of oxime groups in H2L corresponds to amphi-configuration of a ligand and therefore, intramolecular hydrogen bond O...H-O are formed in H2L. The complex cations in compound II are joined in dimers through hydrogen bonds Cl...H-O. The values μeff for I and II are equal to 1.82 and 2.82 μB, respectively.

Ni(II) complexes with optically active bis(menthane), pinano-para-menthane ethylenediaminodioximes and pinano-para-menthane, bis(pinane) propylenediaminodioximes: Synthesis, structures, and properties

Reactions of Ni(NO3)2 · 6H2O) in EtOH(iso-PrOH) with optically active bis(menthane) ethylene-diaminodioxime (H2L1), pinano-para-menthane ethylenediaminodioxime (H2L2), pinano-para-menthane propylenediaminodioxime (H2L3) and bis(pinane) propylenediaminodioxime (H2L4) were used to synthesize [Ni(H2L1)NO3[NO3 · 2H2O (I), [Ni(HL2)]NO3 (II), [Ni(HL3)]NO3 (III), and [Ni(HL4)]NO3 (IV). X-ray diffraction study of paramagnetic complex I (μeff = 3.04 μB and diamagnetic complexes II and III revealed their ionic structures. A distorted octahedral polyhedron N4O2 in the cation of complex I is formed by the N atoms of tetradentate cycle-forming ligand, i.e., the H2L1 molecule, and the O atoms of the NO3− anion acting as a bidentate cyclic ligand. In the cations of complexes II and III, containing a pinane fragment, the coordination core NiN4 has the shape of a distorted square formed on coordination of tetradentate cycle-forming ligands, i.e., anions of the starting dioximes. The structure of diamagnetic complex IV is likely to be similar to the structures of complexes II and III.

Cu(II) complexes with chiral ethylenediaminodioxime and propylenediaminodioxime, the derivatives of monoterpenoid α-pinene: Synthesis and structures

Copper(II) complexes with chiral ethylenediaminodioxime (H2L1) and propylenediaminodioxime (H2L2), the derivatives of terpenoid α-pinene, of the composition [Cu(H2L1)](NO3)2 (I) and [Cu(H2L2)NO3]NO3 (II) are synthesized and studied by X-ray diffraction method. The ionic structures of I and II consist of complex cations [Cu(H2L1)]2+ (I), [Cu(H2L2)NO3]+ (II), and outer-sphere anions NO3−. In the cation of compound I, the Cu2+ ion (C.N.4) coordinates four N atoms of tetradentate cycle-forming ligand H2L1 with anti-configuration. The coordination surrounding of the Cu atom is a trapezoidally distorted square. In the cation of compound II, the Cu2+ ion (C.N.5) coordinates the O atom of monodentate nitro group in addition to four N atoms of tetradentate cycle-forming ligand H2L2. The coordination polyhedron of the Cu atom has the shape of a distorted square pyramid N4O. Coordinated H2L2 molecule has amphi-configuration, which is responsible for the formation of hydrogen bond between the oxime groups. The complex cations and NO3− anions in structures I and II are linked into ionic ensembles by hydrogen bonds.

Reactions of 3-carene, limonene, and α-pinene nitrosochlorides with imidazole, benzotriazole, and indole

The reactions of terpene nitrosochlorides derived from 3-carene, α-pinene, and limonene, with simplest azaheterocycles (imidazole, benzotriazole, and indole) were studied. On the base of these transformations, preparative procedures to access chiral oximes bearing azaheterocyclic moieties in the α-position to the oxime fragment, namely, α-(1H-imidazol-1-yl)-, α-(1H-benzo-[d][1,2,3]triazol-1-yl)-, and α-(1H-indol-3-yl)-substituted terpenic oximes, were developed. Transformations of the studied monoterpene nitrosochlorides into α-substituted oximes proceeded stereoselectively to give in the moderate yields (30–60%) the only stereoisomer arising from the attack of the heterocyclic anion from the less hindered side of the intermediate nitroso olefin generated in situ from nitrosochloride.

Synthesis and structure of optically active compounds [Ni(HL1)]NO3 and [Ni(HL2)]NO3H2O containing anions of diaminodioximes H2L1 and H2L2 derived from α-Pinene and (+)-3-Carene as Ligands

New optically active levorotatory compounds [Ni(HL1)]NO3 (I) and [Ni(HL2)]NO3· H2O (II) containing the anions of chiral diaminodioximes, H2L1 and H2L2, derived from the terpenes ±-pinene and (+)-3- carene, respectively, were synthesized. Complexes I and II were studied by X-ray diffraction. The crystal structures of compounds are ionic, being composed of the [Ni(HL1)]+ or [Ni(HL2)]+ cations and the outer-sphere NO−3 anions. The Ni2+ ion coordinates four N atoms of the tetradentate chelating ligand, the NiN4 coordination unit being shaped like a tetrahedrally distorted square. Compounds I and II are diamagnetic, which corresponds to a low-spin d8 configuration. The NMR spectra of compounds were recorded and analyzed.

Synthesis and properties of copper(II) complexes with a chiral dioxatetraazamacrocyclic ligand based on a natural monoterpene, (+)-3-carene

The copper(II) compounds [CuL](NO3)2 · H2O (I), [CuL](ClO4)2 · H2O (II), CuLCl2 · 3H2O (III), and CuLBr2 · 4H2O (IV), where L is a chiral dioxatetraazamacrocyclic ligand based on the natural monoterpene (+)-3-carene, have been synthesized. According to IR and EPR spectroscopy, L acts as a tetradentate chelating ligand coordinated through the N atoms of the NH and C=N groups. The NO3− anions in I and the ClO4− anions in II are outer-sphere. I and II have a planar coordination core CuN4, III has a CuN4ClO coordination core, and IV has a CuN4Br2 coordination core.