Z. A. Savel’eva

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.

Synthesis and photoluminescence of the chiral compounds [ZnLCl2] · EtOH and ZnLCl2, where L is the (+)-3-Carene derivative containing pyrazoline and quinoline fragments: crystal structure of [ZnLCl2] · EtOH

The following chiral compounds were synthesized: [ZnLCl2] · EtOH (I) and ZnLCl2 (II), where L is the pyrazolin-5-ol derivative obtained from terpene (+)-3-carene. According to the X-ray diffraction data, the crystal structure of compound I is built of acentric molecules of the mononuclear ZnLCl2 complex and EtOH molecules. In molecules of the complex, the Zn2+ ion is coordinated by two N atoms of the bidentate chelating ligand L and two Cl atoms at the vertices of the distorted tetrahedron. The intermolecular contacts and the hydrogen bonds Cl(1)…H-O(1) between the adjacent ZnLCl2 molecules result in the formation of chains parallel to the y axis. The reactant L and solvate I possess weak photoluminescence in the visible spectral range. Complex II exhibits more intense photoluminescence at λmax = 416 and 517 nm.

Cobalt(II) and copper(II) complexes with chiral pyrazolylquinoline, a derivative of terpenoid (+)-3-carene. Catalytic activity in ethylene polymerization reaction

Coordination compounds [CoLCl2] (I), [CuLCl(NO3)] (II), CuL(NO3)2 (III), and CuLCl2 (IV) (where L is a chiral pyrazolylquinoline—a derivative of terpenoid (+)-3-carene) were synthesized. X-ray diffraction data showed that crystal structures I and II are built of mononuclear acentric molecules. In the molecule of complex I, the Co2+ ion coordinates two N atoms of bidentate cycle-forming ligand L and two Cl atoms. The coordination polyhedron of Cl2N2 is a distorted tetrahedron. For complex I, μeff = 4.50 μB, which corresponds to a high-spin configuration d7. In the molecules of II(1), II(2) (which are diastereoisomers of complex II), each Cu2+ ion coordinates two N atoms of bidentate cycle-forming ligand L, the Cl atom, and two O atoms of bidentate cyclic NO3− ion. The ClN2O2 coordination polyhedra are tetragonal pyramids with different degrees of distortion. The structure of complex II consists of supramolecular clusters, i.e., isolated chains incorporating the molecules of II(1) and II(2). The values of μeff for II–IV correspond to the d9 configuration. The results of EPR and IR study suggest that complex III contains the O4N2 polyhedron, whereas complex IV contains the Cl2N2 polyhedron. Complexes I and IV were found to show a high catalytic activity in ethylene polymerization reaction.

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.

Synthesis of binuclear complexes of PdCl2 with chiral α,α′-diamino-meta-xylene dioximes H2L1, H2L2, and H2L3, the derivatives of the terpenes (+)-3-carene, (R)-(+)-limonene, and (S)-(−)-α-pinene. Crystal structure of [Pd2(H2L1)Cl4]

Chiral α,α′-diamino-meta-xylene dioximes H2L1, H2L2, and H2L3 were obtained from the naturally occurring terpenoids (+)-3-carene, (R)-(+)-limonene, and (S)-(−)-α-pinene, respectively. Reactions of these ligands with PdCl2 gave the diamagnetic complexes Pd2(H2L1)Cl4 (I), Pd2(H2L2)Cl4 (II), and Pd2(H2L3)Cl4 (III). According to X-ray diffraction data, the crystal structure of complex I consists of acentric binuclear molecules [Pd2(H2L1)Cl4]. The coordination polyhedron PdN2Cl2 is a square distorted in a tetrahedral manner (trapezium) made up of two N atoms of the tetradentate bridging cyclic ligand H2L1 and two Cl atoms. The fragments PdCl2 in the complex are cis to each other. According to the 1H NMR spectra of complexes I–III in CDCl3, the organic ligands are coordinated through the N atoms; in solution, the complexes exist in several forms.

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.

Crystal structure of solvate [Cd2L2Cl4]·CH2Cl2 (L = pyrazolylquinoline, the derivative of monoterpenoid (+)-3-carene) and photoluminescence of chiral complex CdLCl2

Using the single crystal X-ray diffraction data (150 K, Bruker X8 Apex CCD autodiffractometer, MoKα radiation), the crystal structure of the [Cd2L2Cl4]·CH2Cl2 (L = pyrazolylquinoline, the derivative of monoterpenoid (+)-3-carene) compound is determined. Crystals are monoclinic, unit cell parameters are: a = 10.7005(4) Å, b = 16.8491(4) Å, c = 11.9658(4) Å, β = 93.308(1)°, P21 space group. The structure is formed from discrete acentric molecules of a binuclear [Cd2L2Cl4] complex and uncoordinated CH2Cl2 molecules. The Cd2+ ions coordinate N atoms of bidentate chelating ligands L, which leads to the closure of two five-membered chelate CdN3C rings. The coordination sphere of Cd atoms also includes three Cl atoms (two bridging and one terminal), consequently, two CdCl3N2 coordination sites and a Cd2Cl2 metal ring are formed. The Cl3N2 polyhedra have the form of distorted tetragonal pyramids. The CH2Cl2 molecules located in the channels formed by the complexes are linked with them by weak H-bonds. The excitation spectra of L and the CdLCl2 compound contain bands with λmax of 352 nm and 360 nm respectively. At 300 K and λexcit 350 nm, in the photoluminescence spectrum of L a rather intense broad split band with λmax 372 nm and 386 nm is observed. The photoluminescence spectrum of the CdLCl2 compound contains a broad band with λmax 418 nm. The photoluminescence intensity of this compound is significantly lower than that of L.

Synthesis of binuclear complexes of PdCl2 with chiral ethylenediamine dioxime (H2L1), piperazine dioxime (H2L2), and propylenediamine dioxime (H2L3), the derivatives of the natural monoterpenoid (R)-(+)-limonene. The crystal structures of [Pd2(H2L1)Cl4] and [Pd2(H2L2)Cl4]

The diamagnetic complexes [Pd2(H2L1)Cl4] (I), [Pd2(H2L2)Cl4] (II), and Pd2(H2L3)Cl4(III) with chiral ligands derived from the natural monoterpenoid (R)-(+)-limonene are obtained (H2 L1 is ethylenediamine dioxime, H2L2 is piperazine dioxime, and H2L3 is propylenediamine dioxime). According to X-ray diffraction data, the crystal structures of complexes I and II are composed of binuclear acentric molecules. The coordination polyhedra PdN2Cl2 are trapeziums (squares distorted in a tetrahedral manner) made up of two N atoms of the tetradentate bridging cyclic ligands H2L1 and H2L2 and two Cl atoms. The fragments PdCl2 are trans in the complexes. The 13C and 1H NMR spectra of complexes I and II in CDCl3 also suggest their binuclear structures.

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.

Synthesis of Pd(II) complexes containing the protonated form or molecule of 2-(3,5-dimethylpyrazol-1-yl)-4-methylquinoline (L). The crystal structure of [Pd(HL)Cl3]

The diamagnetic complexes [Pd(HL)Cl3](I) and PdLCl2(II), where L is 2-(3,5-dimethylpyrazol-1-yl)-4-methylquinoline, were obtained. According to X-ray diffraction data, the crystal structure of complex I consists of mononuclear acentric molecules. The coordination polygon PdNCl3 is a distorted square (trapezium) made up of the pyrazole N atom of the monodentate ligand (cation HL+) and three Cl atoms. Complex II seems to contain the square polygon PdN2Cl2.