Zur Kenntnis der Sulfito-kobalt(III)-Ammine. III. Hydrogensulfitokobalt(III)-Ammine

Sulphito Cobalt(III) Ammines. III. Hydrogensulphito Cobalt(III) Ammines Concentrated acids react with [CoSO₃(NH₃)₅]⁺ salts hydrogen- sulphitopentaamminecobalt(III) complexes. [Co(HSO₃)(NH₃)₅]Cl₂, [Co(HSO₃)(NH₃)₅]Br₂ and [Co(HSO₃)(NH₃)₅](HSO₄)₂·H₂O have been isolated. These substances are yellow coloured in contrast to an earlier work which reported red colour. Furthermore, the hydrogensulphitoacidotetreaammine complexes [Co(HSO₃)Cl(NH₃)₄]Cl, [Co(HSO₃)Cl(NH₃)₄]ClO₄·H₂O, [Co(HSO₃)Br(NH₃)₄]Br and [Co(HSO₃) CN(NH₃)₄]Cl habe been prepared. [Co(HSO₃)Br(NH₃)₄]Br is losing spontaneously HBr forming [CoSO₃Br(NH₃)₄]. The neutral complex [Co(HSO₃)SO₃(NH₃)₄]·1/2H₂O has been obtained from cis- NH₄[Co(SO₃)₂(NH₃)₄] and HCl. The absorption spectra in the IR, visible and UV region are reported and discussed. The HSO₃ group is coordinated to Co through the S atom. The Co? S bond is weaker than in the sulphito complexes as concluded from the RAMAN spectrum. In the new complexes, the hydrogensulphito ligand causes a minor trans effect than the sulphito ligand.     

New complexes of tris(2-aminoethanolato-O,N)cobalt(III) sulfates: Synthesis and structure

The reaction of [Co(Etm)₃] · 3H₂O (I) with sulfuric acid affords [Co(HEtm)₃]₂(SO₄)₃ · 4H₂O (II). The change in the synthesis procedure (the direction interaction of cobalt(II) sulfate with β-aminoethanol (HEtm)) makes it possible to isolate [Co(HEtm)₃](SO₄)(HSO₄) · H₂O (III) and {[Co(HEtm)₃][Co(Etm)₃]}₂(SO₄)₃ · 7.75H₂O (IV). The X-ray diffraction analyses of compounds II–IV show that all of them are of the ionic type. In compounds II and III, the ionic structure consists of the [Co(HEtm)₃]₃₊ cations and sulfate anions in a ratio of 2: 3 and 1: 2, respectively. The basic difference in compounds II and III is the different degrees of deprotonation of the acid residues. In complex II, two anions SO ₄ ^2? are doubly deprotonated. In complex III, of the four anions found in the independent part of the unit cell of the sulfate anion two anions are monodeprotonated. In structure IV, two crystallographically independent complexes [Co(HEtm)₃]³⁺ and [Co(Etm)₃] are joined into a dimer through the O-H?O hydrogen bonding.     

Polyol-Metall-Komplexe. 27. Bis-diolato-antimonate(III) mit Guanosin als Diol

Polyol Metal Complexes. 27. Bis-Diolato Antimonates(III ) with Guanosine as the Diol The complex anions of K₃[Sb^III(Guo1,2′,3′H_?3)₂] · 10 H₂O ( 1 ) and [Co(NH₃)₆][Sb^III(Guo1,2′,3′H_?3)₂] · 9 H₂O ( 2 ) are four-coordinate homoleptic bis(diolato)antimonate(III ) species. The guanosine trianions act as carbohydrate ligands through their cis-furanoidic ribosyl moiety, thus forming no nucleobase–metal bonds.     

Synthesis and characterization of [Co(NH3)5NO2][M(NO2)4] (M = Pt, Pd) compounds and their thermolysis products

Compounds [Co(NH₃)₅NO₂][Pd(NO₂)₄] (I) and [Co(NH₃)₅NO₂][Pt(NO₂)₄] · 1.5H₂O (II) have been crystallized from solution. Their crystal structures have been solved, and thermolysis under various conditions studied. The thermolysis products are Co_0.5M_0.5 ordered solid solutions.     

Über die Ammonolyse des Hexamminkobalt(III)-Ions in flüssigem Ammoniak

[Co(NH₃)₆](NO₃)₃ (I) dissolved in liquid NH₃ reacts with 1 equivalent of KNH₂ forming the trinuclear complex [(H₃N)₄Co(NH₂)₂Co(NH₃)₃NH₂Co(NH₃)₅](NO₃)₅ (II) and the binuclear complex [(H₃N)₄Co(NH₂)₂Co(NH₃)₄](NO₃)₄ (III). The cleavage of II with diluted acetic acid + Na₂SO₄ results in the formation of [(H₃N)₄Co(NH₂)₂Co(NH₃)₃ OH₂](SO₄)₂ · 2 H₂O (IV) and [Co(NH₃)₆]³⁺ isolated as the nitrate I. IV could be transformed to III, which gives trans-[Co(NH₃)₄Cl₂]Cl when reacting with a mixture of conc. HCl and H₂SO₄. From the obtained results one may infer that the ammonolysis of I corresponds to the hydrolysis of hexaquoxomplexes of trivalent cations in the course of which polynuclear complexes are also formed.     

Complex Carbonates of Iron(III)

The complex carbonates of iron(III) are shown to be anionic in nature. The solutions containing these complexes show a maximum absorbance at 460 nm. The complex carbonates of iron(III), viz., (i) K₆[Fe₂(OH)₂(CO₃)₅] · H₂O, — (ii) Na₂[Fe₃O₂(OH)₃(CO₃)₂], — (iii) K[Co(NH₃)₆]₂[Fe₃(OH)₄(CO₃)₆], — (iv) K₅[Co(NH₃)₆]₃[Fe₃(OH) ₄(CO₃)₆]₂, — (v) K[Co(NH₃)₆][Fe₂(OH)₄(CO₃)₃], and (vi) NH₄[Co(NH₃)₆][Fe₂(OH)₄(CO₃)₃] are isolated and studied by thermogravimetry. The infrared spectra of these compounds are recorded and probable band assignments made. Besides, the reaction between KHCO₃ and Fe(NO₃)₃ was studied through chemical and physicochemical methods.     

Tetraazidodiammincobaltate(III): Cis-[Co(N3)4(NH3)2]− und [Co(N3)4en]−

Tetra-azidodiamminecobaltates(III): cis-[Co(N₃)₄(NH₃)₂]^? and [Co(N₃)₄en]^? The preparation and the properties of complexes containing the anions cis-[Co(N₃)₄(NH₃)₂]^? and [Co(N₃)₄en]^? are described. The compounds [Co(NH₃)₆][Co(N₃)₄(NH₃)₂ · H₂O], [Co(N₃)₂(NH₃)₄][Co(N₃)₄(NH₃)₂], [As(C₆H₅)₄][Co(N₃)₄en], cis- and trans-[Co(N₃)₂en₂][Co(N₃)₄en] have been isolated.     

Preparation and surface photoelectric properties of Fe(II/III) complexes

Four Fe(II/III) supramolecules, {[Fe(Hpdc)₂(H₂O)₂]·2H₂O} (1), [Fe(HImbc)₂(H₂O)₂] (2), [Fe(phen)₂(CN)₂]·CH₃CH₂OH·2H₂O (3), K[Fe(tp)₂]·SO₄ (4) (H₂pdc = 2,5-Pyridinedicarboxylic acid, H₂Imbc = 4,5-Imidazoledicarboxylic acid, phen = 1,10-phenanthroline, tp⁻ = poly(pyrazolyl)borate), were synthesized by hydrothermal and room temperature stirring methods. They were characterized by single crystal X-ray diffraction, surface photovoltage spectroscopy (SPS), field-induced surface photovoltage spectroscopy (FISPS), electron paramagnetic resonance (EPR), UV–Vis absorption spectra (UV–Vis), infrared spectra (IR) and element analysis. The structural analyses indicate that complex (1) is a supramolecule with 2D structure connected by hydrogen bonds. Complex (2) is a supramolecule with hydrogen-bonded 3D structure. Complexes (3) and (4) are both 1D supramolecules connected by hydrogen bonds. The electronic state of central metal Fe(II) ions in complexes (1) and (2) is d⁶ with FeN₂O₄ coordination mode, lying in weaker distorted octahedral field. The electronic state of Fe(II) ion in complex (3) is d⁶ with Fe(CN)₂N₄ mode in the strong distorted octahedral field. The electronic state of Fe(III) ion in complex (4) is d⁵ with FeN₆ mode, lying in the strong octahedral field. The micro-environment of Fe(II/III) ions in the four complexes is further investigated by EPR. The SPS of four complexes all exhibit photovoltage responses in the range of 300–700 nm. This indicates that they all possess certain photoelectric conversion capability. The effects of component, structure, type of ligands of the complexes, valence state and coordination micro-environment of the central metal ions on the SPS were discussed. Furthermore, the SPS and UV–Vis absorption spectra were interrelated.     

Über die Kristallstrukturen der Cyanokomplexe [Co(NH3)6][Fe(CN)6], [Co(NH3)6]2[Ni(CN)4]3 · 2 H2O und [Cu(en)2][Ni(CN)4]

On the Crystal Structures of the Cyano Complexes [Co(NH₃)₆][Fe(CN)₆], [Co(NH₃)₆]₂[Ni(CN)₄]₃ · 2 H₂O, and [Cu(en)₂][Ni(CN)₄] Of the three title compounds X‐ray structure determinations were performed with single crystals. [Co(NH₃)₆][Fe(CN)₆] (a = 1098.6(6), c = 1084.6(6) pm, R3, Z = 3) crystallizes with the CsCl‐like [Co(NH₃)₆][Co(CN)₆] type structure. [Co(NH₃)₆]₂[Ni(CN)₄]₃ · 2 H₂O (a = 805.7(5), b = 855.7(5), c = 1205.3(7) pm, α = 86.32(3), β = 100.13(3), γ = 90.54(3)°, P1, Z = 1) exhibits a related cation lattice, the one cavity of which is occupied by one anion and 2 H₂O, whereas the other contains two anions parallel to each other with distance Ni…Ni: 423,3 pm. For [Cu(en)₂][Ni(CN)₄] (a = 650.5(3), b = 729.0(3), c = 796.5(4) pm, α = 106.67(2), β = 91.46(3), γ = 106.96(2)°, P1, Z = 1) the results of a structure determination published earlier have been confirmed. The compound is weakly paramagnetic and obeys the Curie‐Weiss law in the range T < 100 K. The distances within the complex ions of the compounds investigated (Co–N: 195.7 and 196.4 pm, Ni–C: 186.4 and 186.9 pm, resp.) and their hydrogen bridge relations are discussed.     

Copper(II), iron(III) and cobalt(III) complexes of the pendent-arm cyclam derivative 6,6,13-trimethyl-13-amino-1,4,8,11-tetraazacyclotetradecane

The interaction of Cu(II), Fe(III) and Co(III) with 6,6,13-trimethyl-13-amino-1,4,8,11-tetraazacyclotetradecane (L ³ ) incorporating a pendent amine group has led to isolation of the new octahedral complexes [Cu(HL ³ )(ClO₄)₂]Cl·H₂O (1), [Fe(L ³ )Cl](S₂O₆)·H₂O (2), [Co(L ³ )Cl](ClO₄)_1.5Cl_0.5·0.25H₂O (3), [Co(HL ³ )Cl₂](ClO₄)₂·H₂O (4) and [Co(L ³ )Cl]₂(S₂O₄)(ClO₄)₂ (5). In (1) the copper ion occupies the macrocyclic cavity of protonated (–NH₃ ⁺) L ³ which is present in its trans-III configuration; weakly bound ClO₄ ^? ligands occupy the axial positions. The X-ray structure of (2) showed that Fe(III) occupies the N₄-macrocyclic cavity of L ³ in a trans-III configuration, with the pendent amine group binding in an axial position. The remaining axial position is occupied by a Cl^? ligand. Chromatography of the product obtained from the reaction of Na₃[Co(CO₃)₃] with L ³ yielded three fractions. Fraction 1 yielded crystals (3) composed of three crystallographically independent species incorporating cations of type [Co(L ³ )Cl]²⁺ with very similar structures; in each case the macrocyclic ring nitrogens of L ³ are bound to the Co(III) in an asymmetric cis-fashion. Fraction 2 yielded the trans-III octahedral cationic complex (4) incorporating L ³ in its protonated form. The Co(III) complex (5) from fraction 3 shows a different coordination arrangement to the products from fractions 1 or 2. The macrocyclic ring coordinates in its trans-III form, but the axial sites in this case are occupied by the pendent-NH₂ group and a Cl^? ligand.     

Computer-aided measurement of kinetic parameters of electrode reactions of cobalt(III)—ammine complexes at mercury electrodes

A computer-aided technique based on Tast polarography is examined for the determination of kinetic parameters of electrode reactions. It is particularly useful for the investigation of unstable species because of the simple and rapid processing of data. Kinetic parameters of cobalt(III)—ammine complexes at mercury electrodes are given for [Co(NH₃)₆]Cl₃, [Co(H₂O)(NH₃)₅](ClO₄)₃, [Co(NO₃)(NH₃)₅](NO₃)₂ [CoF(NH₃)₅](Cl0₄)₂, [Co(C0₃)(NH₃)₅] NO₃ ,cis-[Co(H₂O)₂(NH₃)₄] (Cl0₄)₃ [Co(CO₃)(NH₃)₄] NO₃ · 0.5H₂0, [Co(ox)(NH₃)₄]Cl · H₂0, and NH₄[Co(ox)₂(NH₃)₂] · H₂O, which are obtained in solutions containing 0.1 M acetate buffer and 0.005% gelatin at 25°C.     

Mixtures obtained by reacting trans-(±)-1,2-diaminocyclohexane with acetylacetone in the presence of simple cobalt(II) salts

In the absence of a metal ion, racemic trans-1,2-diaminocyclohexane (trans-(±)DCH) reacts with acetylacetone (acacH) (1:2.5 mole ratio) to form the bisoxoenamine condensation product, boe (1). CoCl₂·6H₂O and Co(ClO₄)₂·6H₂O each react with trans-(±)DCH in air to give complexes containing the oxidised Co(III) ion, [Co((±)DCH)₃]³⁺, which does not subsequently react with added acacH to give a Schiff base complex. Mixtures of complexes are obtained from one-pot reactions involving trans-(±)DCH, a simple Co(II) salt and acacH (1:1:2.5 mole ratio). When CoCl₂·6H₂O is used, the mixed-ligand Co(II) complex [Co((±)DCH)Cl₂] (4) precipitates first and, after a period of weeks, the Co(II) complex (diazH)₂[CoCl₄] (5) (diazH⁺ is a diazepinium cation), the Co(II) complex [Co(boe)Cl₂]_n (6) and the Co(III) complex [Co(acac)₃] (7), co-crystallise from the mother liquor. Using Co(ClO₄)₂·6H₂O in the reaction with trans-(±)DCH and acacH also gives a mixture of products. Complexes 7, the Co(II) complex [Co₂(acac)₄(H₂O)₂][Co(acac)(H₂O)₄]ClO₄·EtOH (8) and the Co(III) complex [Co(acac)₂(±)DCH]ClO₄ (9) co-crystallise. Complexes 1, 5, 7, 8 and 9 were characterised using X-ray crystallography. The major difference between using CoCl₂·6H₂O and Co(ClO₄)₂·6H₂O in reactions involving (±)DCH and acacH is that no DCH/acacH condensation products are identified in the product mixtures when the perchlorate salt is employed.     

Crystal Structures and Hydrogen Bonding of Two Complexes containing the [Ammine‐chlorido‐ethylenediamine‐bis(pyridine)cobalt(III)]2+ Cation

The crystal structures of two classical cobalt(III) complexes comprising the [CoCl(NH₃)(en)(py)₂]²⁺ cation were determined by single‐crystal X‐ray diffraction. Both complexes, dark red [CoCl(NH₃)(en)(py)₂]Cl₂ · H₂O ( 1 ) and purple [CoCl(NH₃)‐(en)(py)₂][HgCl₄] · 1.125H₂O ( 2 ), crystallize in the triclinic space group P1 . In both compounds, the Co atom exhibits a typical octahedral coordination and the configuration index of the complex is OC‐6‐43. In the case of the chloride ( 1 ), the asymmetric unit comprises one formula unit, whereas there are two formula units in the case of the tetrachloridomercurate ( 2 ). Complex cations, anions, and crystal water molecules are interconnected by various N–H ··· N, N–H ··· Cl, N–H ··· O, O–H ··· Cl, and O–H ··· O bridge bonds. As a result, compound 1 features a two‐dimensional layer structure and compound 2 exists as a three‐dimensional network.     

Cobalt(II) complexes with pentadentate Schiff bases 2,6-diacetylpyridine hydrazones: Syntheses and structures

Seven new cobalt(II) complexes based on the Schiff bases, 2,6-diacetylpyridine bis(isonicotinoylhydrazone) (H₂L¹) and 2,6-diacetylpyridine bis(nicotinoylhydrazone) (H₂L²), are synthesized and studied by X-ray diffraction analysis: [Co(H₂L¹)(NCS)₂] · 2.25H₂O (I), [Co(H₂L²)(NCS)₂] · CH₃OH (II), [Co(H₂L²)(NCS)(H₂O)]NCS (III), [Co(H₄L¹)(NCS)₂](NO₃)₂ · 2H₂O (IV), [Co(H₄L¹)(NCS)₂][Co(NCS)₄] · 0.75H₂O (V), [Co(H₄L²)(NCS)₂][Co(NCS)₄] · 1.75H₂O (VI), and [Co(H₂L²)(NCS)(CH₃OH)]₂[Co(NCS)₄] · 2CH₃OH (VII) (CIF files CCDC 941186 (I), 1457906 (Ia), 1457905 (II), 941187 (III), 1457907 (IV), 1457908 (V), 1457909 (VI), and 941188 (VII)). The organic ligands in the complexes act as pentadentate neutral H₂L or doubly protonated (H₄L)²⁺ coordinated through the same set of donor atoms N₃O₂. In all compounds I–VII, the coordination polyhedron of the Co²⁺ ion in a complex with the Schiff bases has a shape of a pentagonal bipyramid. The hydrazones are arranged in the equatorial plane of the bipyramid. Its axial vertices are occupied by the nitrogen atoms of the NCS￣ anions in compounds I, II, and IV–VI and by the nitrogen atoms of NCS￣ and oxygen of the water molecule in compound III or methanol in compound VII. The NO ₃ ^- anions or [Co(NCS)₄]^2￣ complex anions obtained by the reactions are involved along with the NCS￣ anions in the formation of compounds IV–VII.     

cis- und trans-Disulfitotetracyanokobaltate(III)

The preparation and the properties of a series of salts containing the new anion cis-[Co(SO₃)₂(CN)₄]^5? are described. The method of preparation of the trans[Co(SO₃)₂ · (CN)₄^5? complex is improved and the new salt K₄[CoSO₃(CN)₅] · 4H₂O is described. The configuration of the cis- and trans-[Co(SO₃)₂(CN)₄]^5? complexes results from their Raman, IR and UV spectra.     

Synthesis and crystal structure of Co(III) dioximates with the complex anion [SbF6]?

The complexes [Co(DioxH)₂L₂][SbF₆] · nH₂O, where DioxH is dimethylglyoxime monoanion (DioxH^?) or 1,2-cyclohexanedione dioxime (NioxH^?), L is aniline (An) or triphenylphosphine (PPh₃), were isolated from the CoX₂ · nH₂O-NaSbF₆-DioxH₂-L system (X = F or CH₃COO) in aqueous methanol. The complexes were studied by UV, IR, and NMR spectroscopy and by X-ray diffraction. The crystal structure of [Co(DH)₂(An)₂][SbF₆] · H₂O (I) and [Co(NioxH)₂(PPh₃)₂][SbF₆] (II) is stabilized by the electrostatic interactions between the Co(III) complex cations and outer-sphere fluorine-containing anions and by hydrogen bonds between structural units.     

New crystal forms of tris(2-aminoethanolato-O,N)cobalt(III): Structures and properties

Crystal forms of cobalt(III) tris(2-aminoethanolate) hydrates, i.e., red cubic crystals of the composition fac-[Co(NH₂CH₂CH₂O)₃] · 5.44H₂O (fac-I · 5.44H₂O) and blue prismatic crystals of the composition mer-[Co(NH₂CH₂CH₂O)₃] · 3H₂O (mer-I · 3H₂O) were studied by the ⁵⁹Co, ¹³C NMR and X-ray diffraction methods. It was found that mer-[Co(NH₂CH₂CH₂O)₃] · 3H₂O (mer-I · 3H₂O) is a new pseudopolymorphic modification of fac-[Co(NH₂CH₂CH₂O)₃] · 3H₂O (fac-I · 3H₂O), while fac-I · 3H₂O represents a new polymorphic modification of the complex mer-[Co(NH₂CH₂CH₂O)₃] · 3H₂O (mer-I · 3H₂O) described previously. The comparative analysis of the spectra revealed dynamic equilibrium between these geometric isomers; the fac-isomer is stable in aqueous solutions.     

X-ray crystallographic study of crystalline products of interaction of lanthanum(III) nitrate, ammonium tetra(isothiocyanato)diamminechromate(III) and dimethyl sulfoxide in an aqueous solution

A new complex [La(Dmso)₉][Cr(NH₃)₂(NCS)₄]₃ · 4DMSO (I) was synthesized by the reaction of lanthanum(III) nitrate, ammonium tetra(isothiocyanato)diamminechromate(III), and dimethyl sulfoxide and structurally characterized. The crystals are monoclinic, space group C2/c, a = 14.5550(4) ?, b = 25.8826(7) ?, c = 25.5262(6) ?, ?? = 96.5180(10)°, V = 9554.1(4) ?³, Z = 4, ??_calc = 1.467 g/cm³. A freshly precipitated fine crystalline powder corresponds to compound I according to X-ray powder diffraction. However, long-term crystallization leads to formation of at least another four crystalline products: two of them were not characterized because of the poor quality of crystals, the third product was identified as the known complex La(NO₃)₃(Dmso)₄, and the fourth product was identified by X-ray crystallography as the mixed-ligand complex [La(Dmso)₆(NO₃)(NCS)][Cr(NH₃)₂(NCS)₄] · 3Dmso (II) with an island structures. The crystals are monoclinic, space group P2₁/n, a = 18.8026(8) ?, b = 14.9453(5) ?, c = 20.4411(9) ?, ?? = 99.2720(10)°, V = 5669.1(4) ?³, Z = 4, ??_calc = 1.500 g/cm³.     

Effect of heterometallic biscitratogermanates (-stannates) of Co(II) and Ni(II) on the polycondensation and properties of poly(glycol maleate phthalate) copolymers

The ability of heterometallic Ge(IV) and Sn(IV) complexes [Co(H₂O)₆][Ge(HCitr)₂] (I), [Co(H₂O)₆] [Sn(HCitr)₂] (II), [Ni(H₂O)₆][Ge(HCitr)₂] (III), [Ni(H₂O)₆][Sn(HCitr)₂] (IV), [Mg(H₂O)₆][Ge(HCitr)₂] (V), and [Mg(H₂O)₆][Sn(HCitr)₂] (VI) (H₄Citr is citric acid) to activate polycondensation of maleic and phthalic anhydrides with ethylene glycol was studied. Copolymerization of modified poly(glycol maleate phthalate) with triethylene glycol dimethacrylate was performed, and the copolymer characteristics were determined.     

Synthesis and structure investigation of Co(III) complex salts with the perrhenate anion

Complex salts of the composition [Co(NH₃)₆](ReO₄)₃·2H₂O (I), [Co(en)₃](ReO₄)₃ (II), [Co(NH₃)₅H₂O](ReO₄)₃·2H₂O (III), and [Co(NH₃)₅Cl](ReO₄)₂·0.5H₂O (IV) are obtained. Their crystal structures are determined by single crystal XRD. Crystallographic characteristics: (I) a = 9.9797(3) Å, b = 12.6994(3) Å, c = 14.7415(4) Å, β = 102.870(1)°, C2/c space group; (II) a = 8.0615(3) Å, b = 8.4483(4) Å c = 8.8267(4) Å, α = 61.923(2)°, β = 89.552(2)°, γ = 72.295(2)°, P1 space group; (III) a = 8.0086(4) Å, b = 12.9839(6) Å, c = 17.5122(7) Å, β=91.858(1)°, P2₁/n space group; (IV) a = 14.9446(3) Å, b = 14.6562(4) Å, c = 12.2434(4) Å, Cmc2₁ space group.