Rhenium. Part XVI. Ammine and pyridine compounds of zinc and cadmium containing coordinated perrhenate

Summary [Zn(NH₃)₄](ReO₄)₂ and [Cd(NH₃)₄](ReO₄)₂ have been prepared from M(ReO₄)₂ and aqueous ammonia. The tetrapyridine compounds [Zn(py)₄(ReO₄)₂] and [Cd(py)₄(ReO₄)₂] have been obtained by reacting M(NO₃)₂ with aqueous pyridine followed by the addition of HReO₄. Pyrolysis of these complexes gives [Zn(NH₃)₂(ReO₄)₂], [Cd(NH₃)₂(ReO₄)₂], [Zn(py)₂(ReO₄)₂] and [Cd(py)₂(ReO₄)₂] respectively. The kinetics of the decomposition steps: [ML₄(ReO₄)₂] [ML₂(ReO₄)₂] M(ReO₄)₂ have been studied from the t.g.a. curves. I.r. and Raman spectral and x-ray powder diffraction studies indicate that all the pyridine complexes and the two diammine complexes contain coordinated perrhenate, while the two tetrammine complexes contain ionic perrhenate.     

Binding of permanganate anion to pentaammineazidocobalt(III) cation in solution and solid phases: synthesis,characterization, X-ray structure,and genotoxic effects of [Co(NH3)5N3](MnO4)2⋅H2O

A pentaammineazidocobalt(III) complex, [Co(NH₃)₅N₃](MnO₄)₂XH₂O has been synthesized by an one-pot synthesis method. It was characterized by studies such as infrared (IR) and UV-visible spectroscopy. The single crystal X-ray structure analysis revealed that the title complex crystallizes in space group Cc. The cobalt center is six coordinated with slightly octahedral geometry. The supramolecular architecture is also formed by intermolecular N-H…O (anion and H₂O) and Mn-O…O-H hydrogen bonds. The binding property of the cation, [Co(NH₃)₅N₃]²⁺ with the anion, MnO₄^– has also been determined (in solution phase) with the help of UV-visible spectroscopic titrations. Further, the genotoxic effects of KMnO₄, [Co(NH₃)₅N₃]Cl₂ and [Co(NH₃)₅N₃](MnO₄)₂XH₂O were studied using Allium cepa root chromosomal aberration assay and it revealed that the genotoxicity of the newly synthesized complex is 1.97–1.76 fold, which is less compared to KMnO₄. The order of genotoxic potential has been observed to be KMnO₄ > [Co(NH₃)₅N₃](MnO₄)₂XH₂O > [Co(NH₃)₅N₃]Cl₂.     

Complex salts with participation of [Rh(NH<Subscript>3</Subscript>)<Subscript>6</Subscript>]<Superscript>3+</Superscript> cations

Four complex salts with the polyatomic [Rh(NH₃)₆]³⁺ cation are synthesized and studied by X-ray diffraction. The crystallographic characteristics of [Rh(NH₃)₆](WO₄)Cl are determined and the structures of [Rh(NH₃)₆]Cl₃, [Rh(NH₃)₆](ReO₄)₃·2H₂O, and [Rh(NH₃)₆](MoO₄)Cl·3H₂O are solved. The features of mutual packing of the fragments are studied.     

Studies on the Chemistry of Tetraamminezinc(II) Dipermanganate ([Zn(NH3)4](MnO4)2): Low‐Temperature Synthesis of the Manganese Zinc Oxide (ZnMn2O4) Catalyst Precursor

Tetraamminezinc(II) dipermanganate ([Zn(NH₃)₄](MnO₄)₂; 1 ) was prepared, and its structure was elucidated with XRD‐Rietveld‐refinement and vibrational‐spectroscopy methods. Compound 1 has a cubic lattice consisting of a 3D H‐bound network built from blocks formed by four MnO anions and four [Zn(NH₃)₄]²⁺ cations. The other four MnO anions are located in a crystallographically different environment, namely in the cavities formed by the attachment of the building blocks. A low‐temperature quasi‐intramolecular redox reaction producing NH₄NO₃ and amorphous ZnMn₂O₄ could be established occurring even at 100°. Due to H‐bonds between the [Zn(NH₃)₄]²⁺ cation and the MnO anion, a redox reaction took place between the NH₃ and the anion; thus, thermal deammoniation of compound 1 cannot be used to prepare [Zn(NH₃)₂](MnO₄)₂ (contrary to the behavior of the analogous perrhenate (ReO ) complex). In solution‐phase deammoniation, a temperature‐dependent hydrolysis process leading to the formation of Zn(OH)₂ and NH₄MnO₄ was observed. Refluxing 1 in toluene offering the heat convecting medium, followed by the removal of NH₄NO₃ by washing with H₂O, proved to be an easy and convenient technique for the synthesis of the amorphous ZnMn₂O₄.     

Über Tetramminmetallchalkogenometallate

Zusammenfassung Es wird über die Darstellung sowie schwingungsspektroskopische und röntgenographische Untersuchung von Chromaten, Molybdaten, Wolframaten, Permanganaten und Perrhenaten der komplexen Kationen [Cu(NH₃)₄]²⁺, [Zn(NH₃)₄]²⁺ und [Cd(NH₃)₄]²⁺ berichtet. Die Strukturdaten sowie IR-Spektren werden diskutiert.

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Tetramminmetallchalcogenometallates

The preparation, the vibrational spectra and structure data of chromates, molybdates, tungstates, permanganates and perrhenates of the complex cations [Cu(NH₃)₄]²⁺, [Zn(NH₃)₄]²⁺ and [Cd(NH₃)₄]²⁺ are reported. The structural data and the infrared spectra are discussed.

     

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.     

Synthesis, crystal structure, hydrogen bonding and spectroscopy of transition-metal complexes with the ligand (N,N′-bis(2-pyridylmethyl)-1,3-propanediamine)

Six mononuclear complexes are reported with the tetradentate ligand N,N′-bis(2-pyridylmethyl)-1,3-propanediamine, (abbreviated as pypn) i.e. [Cu(pypn)(ClO₄)₂](H₂O)_1/2 (1), [Fe(pypn)Cl₂](NO₃) (2), [Zn(pypn)Cl](ClO₄) (3), [Co(pypn)(NCS)₂](ClO₄) (4), [Co(pypn)(N₃)₂](ClO₄) (5), [Zn(pypn)(NCS)₂] (6). The synthesis and X-ray crystal structures of all six compounds and their spectroscopic properties are presented.The geometry of the Cu²⁺, Co³⁺, Zn²⁺, Fe³⁺ ions is essentially octahedrally based, with the mm conformation (for Cu) and m_sf conformations for the other 3 metal ions; in compound 3 the geometry around the Zn²⁺ is distorted trigonal bipyramidal. The stabilisation of the crystal lattices is maintained by interesting, relative strong hydrogen bonds.     

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.     

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.     

The infrared spectra of imidazole complexes of first transition series metal(ii) nitrates and perchlorates

The IR spectra (4000–4140 cm^?1 ) of the twelve imidazole (Him) complexes [M(Him)₆] (NO₃)₂ (M = Co, Ni, Zn); [M(Him)₆](ClO₄)₂ (M = Mn, Fe, Co, Ni); [Zn(Him)_s](ClO₄)₂; [Cu(Him)₄X₂] (X = NO₃, ClO₄); [Zn(Him)₄(NO₃)₂]; [Zn(Him)₄](ClO₄)₂ and their deuterated analogues are discussed. The ratio between the frequencies of corresponding bands in the deuterated and undeuterated species is used to assign the internal imidazole vibrations. The internal modes of the NO₃^? and ClO₄^? ions are discussed in relation to the known or proposed structures of the complexes. The metal-ligand vibrations are assigned on the grounds of the shifts which occur on imidazole deuteration and metal ion substitution.     

Activity and Osmotic Coefficients from the Emf of Liquid Membrane Cells. X. Tris(Ethylenediamine) Cobalt(III) Nitrate, Perchlorate, and Chloride

Activity coefficients of [Co(en)₃](NO₃)₃ and [Co(en)₃](ClO₄)₃, to be compared with [Co(en)₃]Cl₃ and the corresponding lanthanum salts previously studied, are determined. [Co(en)₃]Cl₃ data are revised. Ion interaction strengths vary in the same order found for La³⁺, i.e., as if nitrate and perchlorate ions were of smaller and larger size, respectively, than chloride ions; however, the differences are much smaller than in lanthanum salts. Tris(ethylenediamine)cobalt III and lanthanum nitrate, chloride, and perchlorate—like the corresponding hexacyanoferrate(III) and hexacyanocobaltate(III) salts, but contrary to sulfate salts—behave as if [Co(en)₃]³⁺ were smaller in size than La³⁺. In the dilute regions, [Co(en)₃](NO₃)₃ displays negative deviations from the limiting slope, a kind of behavior typical for 2:2, 2:3, 3:2, and 3:3 electrolytes, but unnoticed earlier for 3:1 or 1:3 electrolytes. Pitzer's equation parameters able to provide accurate activity and osmotic coefficients for [Co(en)₃](NO₃)₃, [Co(en)₃](ClO₄)₃, and, revised, [Co(en)₃]Cl₃ are reported.     

Darstellung und Elektronenspektren neuer Trithiocarbonato-Komplexe; Struktur,Eigenschaften und Photoelektronenspektren von Ni(NH3)3CS3 und Zn(NH3)2CS3

Preparation and Electronic Spectra of new Trithiocarbonato Complexes; Structure, Properties, and Photoelectronic Spectra of Ni(NH₃)₃CS₃ and Zn(NH₃)₂CS₃ The complex anions [Zn(CS₃)₂]^2?, [Cd(CS₃)₂]^2?, [Co(CS₃)₃]^3?, [Cr(CS₃)₃]^3?, [As(CS₃)₃]^3?, [Sb(CS₃)₃]^3?, [Bi(CS₃)₃]^3?, [Sn(CS₃)₂]^2?, and [Cu(CS₃)] could be isolated as tetraphenylphosphonium and tetraphenylarsonium salts. From the electronic spectra of the transition metal complexes it follows that the CS ion exhibits, in comparison with other sulfur containing ligands, relatively large Δ-values and only a small nephelauxetic effect (e.g. in [Cr(CS₃)₃]^3?: Δ = 16.0 kK; β₃₅ = 0.57). The trithiocarbonate ion in all the above complexes acts as a bidentate ligand and forms fourmembered ring systems CS₂M. Further it was proved by means of infrared, electronic and photoelectronic spectra that the structure of “Ni(NH₃)₃CS₃” is [Ni(NH₃)₆][Ni(CS₃)₂] whereas Zn(NH₃)₂CS₃ has not such an ionic structure.     

X-ray diffraction study of the monoclinic modification of [Cu(NH<Subscript>3</Subscript>)<Subscript>4</Subscript>](ReO<Subscript>4</Subscript>)<Subscript>2</Subscript> in the range 100-410 K

The monoclinic modification of [Cu(NH₃)₄](ReO₄)₂ complex salt in the range 100-410 K is studied by single crystal X-ray diffraction. The crystallographic data for 300 K are as follows: a = 10.6123(3) Å, b = 7.5443(2) Å, c = 15.2261(4) Å, β = 108.406(1)°, V = 1156.67(5) ų, space group Р2₁/n, Z = 4, d_x = 3.623 g/cm³. The coordination environment of the Cu atom, being a distorted square formed by four nitrogen atoms with Cu–N of 1.997-2.018 Å, is completed by the contacts with two oxygen atoms Cu…O of 2.472 Å and 2.598 Å. The comparative crystal chemical analysis with the triclinic modification of [Cu(NH₃)₄](ReO₄)₂ known in the literature is performed.     

A theoretical insight into the role of counter anions and their interactions in nitropentaamminecobalt(III) toward linkage isomerism-induced photochemical motion

Density functional theory (B3LYP, B3LYP-D3, wB97XD, M062X, and M06L) and ab initio methods (MP2 and CCSD(T)) in conjunction with 6-31+G(d,p) and LanL2DZ were employed to investigate the interaction energies between [Co(NH₃)₅NO₂]²⁺ linkage isomers and chloride and nitrate in both gas phase and solid state. The nature of the chemical bonding has been analyzed by means of the atoms in molecules, electron density shift, natural bond orbitals, symmetry adapted perturbation theory, and energy decomposition analysis. The electronic structures of the two lowest laying singlet states (S_o and S₁) of [Co(NH₃)₅NO₂](NO₃)Cl isomers were also investigated using CASSCF(6,6) with LanL2DZ and 6-31G(d) basis sets. Our results show that [Co(NH₃)₅NO₂]²⁺ linkage isomers interact more strongly with chloride than nitrate. The structures of [Co(NH₃)₅NO₂](NO₃)Cl linkage isomers and their relative stabilities were examined in gas phase and in solid state and confirmed the nitro-complex as the most stable following by a viable intermediate endo-complex. Study of the nitro-nitrito linkage isomerization in [Co(NH₃)₅NO₂](NO₃)Cl revealed that anions form strong electrostatic bonds with [Co(NH₃)₅NO₂]²⁺ leading to decrease in an activation energy compared to the [Co(NH₃)₅ONO]²⁺ isomers. A concerted action of ionic interactions and hydrogen bonds are suspected of regulating the isomerization in solid state. Assessment of various DFT methods with respect to CCSD(T) suggests M062X suitable method for [Co(NH₃)₅NO₂](NO₃)Cl linkage-isomerization study. Potential energy surface calculations at the CASSCF/6-31G(d) level of theory shows that the conical intersection (S₁/S_o) might play an important role in the photoisomerization of [Co(NH₃)₅NO₂](NO₃)Cl.     

Studies on the Chemistry of [Cd(NH3)4](MnO4)2. A Low Temperature Synthesis Route of the CdMn2O4+x Type NOx and CH3SH Sensor Precursors

Abstract. [Tetraamminecadmium(II)] bis(permanganate) ( 1 ) was prepared and its crystal structure was elucidated with XRD‐Rietveld refinement and vibrational spectroscopic methods. Compound 1 has a cubic lattice consisting of a 3D hydrogen‐bonded network built as four by four distorted tetrahedral blocks of [Cd(NH₃)₄]²⁺ cations and MnO₄^– anions, respectively. The other four permanganate ions are located in a crystallographically different environment, placed in the cavities formed by the attachment of the building blocks. A low‐temperature (≈100 °C) solid phase quasi‐intramolecular redox reaction producing ammonium nitrate and amorphous CdMn₂O₄ could be established. Neither solid phase nor aqueous solution phase thermal deammoniation of compound 1 can be used to prepare Cd(MnO₄)₂ and [Cd(NH₃)₂(MnO₄)₂]. During deammoniation of compound 1 in aqueous solution a precipitate consisting of Cd(OH)₂ forms. Additionally, solid MnO₂ and ammonium permanganate (NH₄MnO₄) forms. The solid phase deammoniation reaction (toluene used as heat convecting medium) with subsequent aqueous leaching of the ammonium nitrate formed has proved to be an easy and convenient technique for the synthesis of amorphous CdMn₂O_4+x type NO_x and MeSH sensor precursors. The 1 ‐ D perdeuterated complex was also synthesized to distinguish the N–H(D) and O–H(D) fragment signals in the TG‐MS spectra and to elucidate the vibrational characteristics of the overlapping Mn–O and Cd–N frequencies.     

Effect of alkali metals and metal-ammonia complexes on electroosmosis,effective field strength,and resolution in the separation of diuretics by CZE

The counter ion in CZE separation systems affects resolution, effective field strength and electroosmosis. Alkali metals (lithium, sodium, potassium, and cesium), the ammonium ion, and several complexes of metals with ammonia ([Ag(NH₃)₂]⁺, [Cu(NH₃)₄]²⁺, [Zn(NH₃)₄]²⁺, [Cd(NH₃)₄]²⁺, [Ni(NH₃)₆]²⁺, and [Co(NH₃)₆]²⁺) have been studied for their effect on the separation of diuretics. With the alkali metals the electroosmotic flow velocity decreased and the effective field strength and resolution increased as the hydrated radius of the alkali metal decreased. All the metal-ammonia complexes except that with silver greatly reduced the electroosmotic flow velocity (V_eo) and had only a slight effect on the effective field strength (E_eff). Because these complexes had a negligible effect on the ionic strength of the buffer, they enabled high separating power to be maintained during the separation, and hence the use of more energy in the separation system. This yielded better resolution of the compounds, but the analysis time was then compromised. A simultaneous reduction in capillary length and V_eo while maintaining the high voltage enabled increased resolution without an increase in analysis time. The ability to control V_eo by adding small concentrations (< 100 μM ) of metal complexes to the buffer solution makes it possible to adjust the analysis time and capillary length independently while employing high separation power.     

Metal solid solutions obtained by thermolysis of Pt and Re salts. Crystal structure of [Pt(NH3)4](ReO4)2

A complex salt of tetraammineplatinum(II) perrhenate [Pt(NH₃)₄](ReO₄)₂ has been synthesized. Crystal data: a = 5.1847(6) Å, b = 7.7397(8) Å, c = 7.9540(9) Å, α = 69.531(3)°, β = 79.656(3)°, γ = 77.649(3)°, V = 290,19(6) ų, space group $P\bar 1$ , Z = 1, d _x = 4.370 g/cm³. The products of decomposition of [Pt(NH₃)₄](ReO₄)₂ in a hydrogen atmosphere were investigated using X-ray phase analysis. In definite temperature modes, these are Pt_0.33Re_0.67 solid solutions based on Re with hcp cell parameters a = 2.76 Å, c = 4.42 Å. The products of thermolysis obtained from other precursor complex salts containing both Pt and Re were investigated. Thus Pt_0.75Re_0.25 solid solution with a = 3.905(3) Å was obtained from (NH₄)₂[ReCl₆]_0.25[PtCl₆]_0.75.     

[Ag(NH3)2]Ag(OsO3N)2: a new nitridoosmate(VIII)

Dark brown single crystals of [Ag(NH₃)₂]Ag(OsO₃N)₂ were obtained from the reaction of Ag₂CO₃, OsO₄, and NH₃ in aqueous solution. The crystal structure was solved in the monoclinic space group C2/m, with the following unit-cell dimensions: a=1962.5(3), b=633.1(1), c=812.6(1) pm, β=96.71(1)°. The final reliability factor was R=0.0256 for 1034 reflections with I>2σ(I). Linear [Ag(NH₃)₂]⁺ ions are present oriented perpendicular to the [010] direction, leading to short Ag⁺-Ag⁺ distances of 316 pm. A second type of Ag⁺ ions in the crystal structure present coordination number “6+1” and are surrounded by oxygen and nitrogen atoms of the nitridoosmate groups. Within the first of the two crystallographically distinguishable anions one can clearly differentiate between oxygen and nitrogen atoms while the second one exhibits a N/O disorder over two positions. The infrared spectrum of [Ag(NH₃)₂]Ag(OsO₃N)₂ shows the typical absorptions which can be attributed to the complex anions and the NH₃ ligands.     

Spektroskopische Untersuchung von Tetramminzink-und Tetrammincadmium-tetrachloroplatinat(II)

Zusammenfassung Die Festkörperelektronenspektren sowie die Infrarotspektren (im Bereich 4000–100 cm^–1) der Verbindungen [Zn(NH₃)₄]-PtCl₄ und [Cd(NH₃)₄]PtCl₄ werden gemessen und kurz besprochen.

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Spectroscopic investigation of tetramminzinc and tetrammincadmium tetrachloroplatinates(II)

The reflectance-electronic and IR-spectra of solid [Zn(NH₃)₄]PtCl₄ and [Cd(NH₃)₄]PtCl₄ are measured and briefly discussed.

     

The catalytic effect of transition metal-ion ammine complexes on the decomposition of hydrogen peroxide in the presence of Dower-50W resin in aqueous medium

Summary The kinetics of the catalytic decomposition of hydrogen peroxide was studied in the presence of Dowex-50W resin in the form of some transition metal-ion ammine complexes in an aqueous medium. The transition metal-ions, Co²⁺, Ag⁺, Cd²⁺ and Zn²⁺ were chosen in this study and the rate constants (per gram of dry resin) were evaluated at various resin weights in the 25–40°C range. A coloured compound (peroxo-metal complex), which formed at the beginning of the reaction in each case, was found to contain the catalytic active species. Probable mechanisms for the reactions are proposed. The activation energy and the change in the entropy of activation increased in the following sequence: [Ag(NH₃]₂]⁺< [Cd(NH₃)₆]²⁺<[Co(NH₃)₆]²⁺<[Zn(NH₃)₆]²⁺, which is also the probability sequence for the formation of the activated complex.