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Vol 44, No 6 (2018)
- Year: 2018
- Articles: 6
- URL: https://journals.rcsi.science/1070-3284/issue/view/13354
Article
1D-Bromobismuthates of Dipyridinoalkane Derivatives
Abstract
The following bromobismuthates of organic cations (dipyridinoalkane derivatives) are synthesized and characterized: (4-NH2PyC5)BiBr5 (I), (2-MePyC2)BiBr5 (II), (2-NH2PyC10)BiBr5 · 0.65H2O (III), (2-NH2PyC10)4H5O2(BiBr6)3 (IV), (2-NH2PyС6)2KBi2Br11 (V), (2-NH2PyC6)H3OBiBr6 · 2.33H2O (VI), and (2-NH2PyC6)3(BiBr6)2 · CH3CN (VII). Three compounds obtained (I–III) contain the zigzag 1D chain (BiBr5)n. A new type of 1D chains, (KBi2Br11)n, is found in the structure of compound V. Pseudo-1D chains of BiBr63− anions can be observed in the 3D structures of compounds IV, VI, and VII. The crystallographic data were deposited with the Cambridge Crystallographic Data Centre (CIF files CCDC 1569478 (I)–1569484 (VII), respectively).
373-379
Gallium Complexes with Acenaphthene-1-Imino-2-one: Synthesis and Reactivity
Abstract
The reduction of acenaphthene-1-(2,6-diisopropylphenyl)imino-2-one (Dpp-Mian) by gallium in the presence of iodine primarily results in a bis(ligand) paramagnetic derivative [(Dpp-Mian)2GaI] and then to a dimeric diamagnetic complex [(Dpp-Mian)GaI]2, the reaction of which with PhC≡CH gives a cycloaddition product [{Dpp-Mian(HC=CPh)}GaI]2. The new compounds are characterized by IR spectroscopy and 1H NMR spectroscopy. The structures of complexes (Dpp-Mian)2GaI and [{Dpp- Mian(HC=CPh)}GaI]2 are determined by X-ray structure analysis (CIF files CCDC nos. 1571860 and 1571861, respectively). The catalytic activity tests for compounds [(Dpp-Mian)GaI]2 and [{Dpp-Mian(HC=CPh)}GaI]2 are conducted in the reactions of 4-chloroaniline with phenylacetylene and carbodiimide and in the reaction of phenylacetylene with 1-naphthol.
380-387
Binuclear Cyclic Silver(I) Complex with the Anion of 4-[(2-Diphenylphosphanylphenyl)methyleneamino]benzoic Acid: Synthesis, Structure, and Optical Properties
Abstract
4-[(2-Diphenylphosphanylphenyl)methyleneamino]benzoic acid (HL) is obtained by the condensation of o-diphenylphosphinobenzaldehyde and p-aminobenzoic acid. The reaction of AgNO3 and HL affords complex [Ag2L2] · H2O (I). The structure of complex I is determined by X-ray structure analysis (CIF file CCDC 1575064), and its reflectance and luminescence spectra are studied. Binuclear complex I is a cyclic molecule in which each of two silver(I) atoms coordinates one phosphorus atom and one oxygen atom of two bridging anions L. Compound I is characterized by emission in a range of 430–740 nm at λexc = 340 and 395 nm.
388-392
Synthesis and Structure of Different-Metal Different-Ligand Germanium(IV) and Cobalt(II) or Copper(II) Complexes with 1-Hydroxyethylidenediphosphonic Acid and 1,10-Phenanthroline
Abstract
Different-metal different-ligand complexes [{Co(Phen)3}2{Co(Phen)(H2O)4}2][{Ge(μ-OH)(μ- Hedp)}6Cl2] (I), [{Cu(Phen)2(H2O)}2(HPhen)2][Ge(μ-OH)(μ-Hedp)]6 · 20H2O (II) (H4Hedp = 1-hydroxyethylidenediphosphonic acid, Phen = 1,10-phenanthroline) were synthesized and studied by X-ray diffraction. According to X-ray diffraction data (CIF files CCDC nos. 1573112 (I), 1573113 (II)), compounds I and II are cation–anion type complexes in which the anions are represented by {[Ge(μ-OH)(μ-Hedp)]6}6– and, in the case of I, two additional Cl– ions, while the cations are [Co(Phen)3]2+, [Co(Phen)(H2O)4]2+ in I and [Cu(Phen)2(H2O)]2+, HPhen+ in II. In the crystals of compounds I and II, the cations, anions, and water molecules are combined by numerous intermolecular hydrogen bonds, giving rise to a 3D network.
393-399
Europium and Ytterbium Complexes with the Redox Active Acenaphthene-1,2-Diimine Ligand
Abstract
The oxidation of [(Dpp-Bian)Eu(Dme)2] (I) (Dpp-Bian is the 1,2-bis[(2,6-diisopropylphenyl) imino]acenaphthene dianion, Dme = 1,2-dimethoxyethane), prepared in situ, with 0.5 mol equiv. of iodine in Thf gives europium(II) dimer, [(Dpp-Bian)Eu(μ-I)(Thf)2]2 (II) (Thf = tetrahydrofuran), with the Dpp-Bian ligand as radical anion. The exchange reaction of II with potassium dithiocarbamate affords europium( II) dimer, [(Dpp-Bian)Eu[SC(S)NMe2](Thf)]2 (III), which also contains the Dpp-Bian radical anion. However, the oxidation of the ytterbium complex [(Dpp-Bian)Yb(Dme)2] (IV) with 0.5 mol equiv. of [Me2NC(S)S]2 gives the monomeric product [(Dpp-Bian)Yb[SC(S)NMe2](Dme)] (V), in which Dpp-Bian is still the dianion and the ytterbium atom is oxidized to the trivalent state. The reaction of II with potassium thiocyanate gives europium(II) isothiocyanate complex with the radical anion diimine ligand [(Dpp-Bian)Eu(NCS)(Dme)2] (VI). The molecular structures of complexes II, III, V, and VI were determined by X-ray diffraction (CIF files CCDC 1576687–1576690, respectively).
400-409
Spontaneous Association of the Terbium Cyclopentadienyl Complexes under Controlled Hydrolysis
Abstract
Controlled hydrolysis of the terbium cyclopentadienyl complexes results in the formation of the heteroligand tetranuclear terbium complex [{Tb(η5-C5H5)}3{Tb(THF)3}(μ3-Cl)(μ2-Cl)6(μ4-O)] (I), the recrystallization of which from tetrahydrofuran (THF) gives solvatomorph I · 0.5THF (Ia). According to the X-ray structure analysis data (CIF files CCDC 1569329 (I) and 1569330 (Ia)), the complexes are tetrahedral with the μ4-bridging O2– anion at the center of the tetrahedron. The cyclopentadienyl ligand in complex I is shown to act as an “antenna” providing luminescence of the complex.
410-414