μ-Nitro-μ-hydroxo-bis(tetramminkobalt(III))-Komplexe

The preparation and the properties of 7 salts containing the complex cation [Co₂{NO₂, OH}(NH₃)₈]⁴⁺ are described. Furthermore, a di-μ-hydroxo complex of the composition [Co₂{OH}₂NO₂(NH₃)₇](ClO₄)₃ · H₂O has been prepared.     

μ-Nitro-di-μ-hydroxo-bis[trinitro-kobaltat(III)]-Komplexe

4 complexes containing the anion [Co₂{NO₂(OH)₂}(NO₂)₆]^3? are described. The infrared and Raman spectra are reported and discussed.     

Di-μ-sulfato-μ-hydroxo-bis[triamminkobalt(III)]- und Di-μ-selenato-μ-hydroxo-bis[triamminkobalt(III)]-Komplexe

Preparation and properties of two new complexes containing the cations [Co₂{(SO₄)₂(OH)}(NH₃)₆]⁺ and [Co₂{(SeO₄)₂(OH)}(NH₃)₆]⁺ are described. The absorption spectra in the infrared. visible and ultraviolet region are reported and discussed.     

Über das Tri(phosphorano)borazinium-Monokation [H3B3(NPEt3)3Cl2]+. Kristallstrukturen von Me3SiNPR3 · BH3 (R = Et,Ph), [H3B3(NPEt3)3Cl1,85Br0,15]Br · CCl4 und des Hydrolyseproduktes NH4[B5O6(OH)4] · 2 H2O

On the Tri(phosphorano)borazinium Monocation [H₃B₃(NPEt₃)₃Cl₂]⁺. Crystal Structures of Me₃SiNPR₃ · BH₃ (R = Et, Ph), [H₃B₃(NPEt₃)₃Cl_1.85Br_0.15]Br · CCl₄, and of the Product of Hydrolysis NH₄[B₅O₆(OH)₄] · 2 H₂O The crystal structures of the donor-acceptor complexes of the silylated phosphanimines with borane which are suitable as educts for the synthesis of tri(phosphorano)borazinium ions, Me₃SiNPR₃ · BH₃ (R = Et, Ph), are described. After addition of CCl₄ the reaction of Me₃SiNPEt₃ with HBBr₂ · SMe₂ in CH₂Cl₂ leads to the tri(phosphorano)borazinium monocation [H₃B₃(NPEt₃)₃Cl₂]⁺, which is characterized crystallographically as [H₃B₃ · (NPEt₃)₃Cl_1.85Br_0.15]Br · CCl₄. It complements the series of the tri(phosphorano) cations [H₃B₃(NPEt₃)₃]³⁺ and [H₄B₃(NPEt₃)₃]²⁺ by the monocation. NH₄[B₅O₆(OH)₄] · 2 H₂O can be isolated as product of hydrolysis of the tri(phosphorano)borazinium ions; its crystal structure is redetermined, because in the literature it is based on a wrong space group. Me₃SiNPEt₃ · BH₃ ( 1 ): Space group P1, Z = 4, lattice dimensions at 213 K: a = 710.9(4), b = 1465.9(3), c = 1536.0(3) pm, α = 107.05°, β = 99.40(3)°, γ = 97.41(3)°; R = 0.0740. Me₃SiNPPh₃ · BH₃ ( 2 ): Space group P2₁/c, Z = 4, lattice dimensions at 203 K: a = 934.6(1), b = 1398.6(1), c = 1626.1(1) pm, β = 103.52(1)°; R = 0.0556. [H₃B₃(NPEt₃)₃Cl_1.85Br_0.15]Br · CCl₄ ( 3 ): Space group P2₁/n, Z = 4, lattice dimensions at 223 K: a = 1237.9(3), b = 1214.1(3), c = 2402.4(4) pm, β = 93.52(1)°. 3 holds a B₃N₃ six-membered ring in a distorted boat conformation. NH₄[B₅O₆(OH)₄] · 2 H₂O ( 4 ): Space group Aba2, Z = 4, lattice dimensions at 273 K: a = 1131.3(1), b = 1103.0(1), c = 923.0(1) pm; R = 0.0564.     

Kinetics and Mechanism of Oxidation of S2O32− by a Co‐Bound μ‐Amido‐μ‐Superoxo Complex

In acetate buffer media (pH 4.5–5.4) thiosulfate ion (S₂O₃^2?) reduces the bridged superoxo complex, [(NH₃)₄Co^III(μ‐NH₂,μ‐O₂)Co^III(NH₃)₄]⁴⁺ ( 1 ) to its corresponding μ‐peroxo product, [(NH₃)₄Co^III(μ‐NH₂,μ‐O₂)Co^III(NH₃)₄]³⁺ ( 2 ) and along a parallel reaction path, simultaneously S₂O₃^2? reacts with 1 to produce the substituted μ‐thiosulfato‐μ‐superoxo complex, [(NH₃)₄Co^III(μ‐S₂O₃,μ‐O₂)Co^III(NH₃)₄]³⁺ ( 3 ). The formation of μ‐thiosulfato‐μ‐superoxo complex ( 3 ) appears as a precipitate which on being subjected to FTIR shows absorption peaks that support the presence of Co(III)‐bound S‐coordinated S₂O₃^2? group. In reaction media, 3 readily dissolves to further react with S₂O₃^2? to produce μ‐thiosulfato‐μ‐peroxo product, [(NH₃)₄Co^III(μ‐S₂O₃,μ‐O₂)Co^III(NH₃)₄]²⁺ ( 4 ). The observed rate (k₀) increases with an increase in [T_Thio] ([T_Thio] is the analytical concentration of S₂O₃^2?) and temperature (T), but it decreases with an increase in [H⁺] and the ionic strength (I). Analysis of the log A_t versus time data (A is the absorbance of 1 at time t) reveals that overall the reaction follows a biphasic consecutive reaction path with rate constants k₁ and k₂ and the change of absorbance is equal to {a₁ exp(–k₁t) + a₂ exp(–k₂t)}, where k₁ > k₂.     

Hydrothermal syntheses,crystal structures and thermal stability of two divalent metal phosphonates with a layered and a 3D structure

Two new divalent metal phosphonates, [Cu₂{CH₃C(OH)(PO₃)₂}(H₂O)₂]?·?0.5H₂O (1) and [NH₃CH₂CH₂NH₃][Zn₃{CH₃C(OH)(PO₃)₂}₂(H₂O)]?·?H₂O (2), have been hydrothermally synthesized and characterized by single-crystal X-ray diffraction as well as with infrared spectroscopy, elemental analysis and thermogravimetric analysis. The structure of 1 comprises [Cu₃(hedp)₂]^2? layers connected by [CuO₄] units to form a 3D open-framework structure with a one-dimensional channel system along the b axis. In 2, the connections of alternately arranged [ZnO₄] tetrahedra, [ZnO₆] octahedra and [CPO₃] tetrahedra via vertex-sharing result in a 2D layered structure. The protonated ethylenediamine cations and water molecules are located between adjacent layers.     

Kalium-μ-dithio-bis(pentacyanokobaltat(III)) und Kalium-μ-diseleno-bis(pentacyanokobaltat(III))

Potassium-μ-dithio-bis(pentacyanocobaltate(III)) and Potassium-μ-diseleno-bis(pentacyanocobaltate(III)) The oxidation of [Co(CN)₅]^3? by sulfur or selenium leads to the complexes [Co₂S₂(CN)₁₀]^6? and [Co₂Se₂(CN)₁₀]^6?, respectively, which have been isolated as potassium salts K₆[Co₂S₂(CN)₁₀] · 4 H₂O and K₆[Co₂Se₂(CN)₁₀] · 5 H₂O. The μ-dithio complex has also been formed from [Co(CN)₅]^3? with polysulfide, from [CoOH(CN)₅]^3? with H₂S + O₂ and from [Co₂O₂(CN)₁₀]^6? with H₂S. As shown by their vibrational spectra the new complexes contain bridges Co? S? S? Co and Co? Se? Se? Co, respectively.     

Isotype Strukturen einiger Hexaamminmetall(II)-halogenide von 3d-Metallen: [V(NH3)6]I2, [Cr(NH3)6]I2, [Mn(NH3)6]Cl2, [Fe(NH3)6]Cl2, [Fe(NH3)6]Br2, [Co(NH3)6]Br2 und [Ni(NH3)6]Cl2

The Structures of some Hexaammine Metal(II) Halides of 3 d Metals: [V(NH₃)₆]I₂, [Cr(NH₃)₆]I₂, [Mn(NH₃)₆]Cl₂, [Fe(NH₃)₆]Cl₂, [Fe(NH₃)₆]Br₂, [Co(NH₃)₆]Br₂ and [Ni(NH₃)₆]Cl₂ Crystals of yellow [V(NH₃)₆]I₂ and green [Cr(NH₃)₆]I₂ were obtained by the reaction of VI₂ and CrI₂ with liquid ammonia at room temperature. Colourless crystals of [Mn(NH₃)₆]Cl₂ were obtained from Mn and NH₄Cl in supercritical ammonia. Colourless transparent crystals of [Fe(NH₃)₆]Cl₂ and [Fe(NH₃)₆]Br₂ were obtained by the reaction of FeCl₂ and FeBr₂ with supercritical ammonia at 400°C. Under the same conditions orange crystals of [Co(NH₃)₆]Br₂ were obtained from [Co₂(NH₂)₃(NH₃)₆]Br₃. Purple crystals of [Ni(NH₃)₆]Cl₂ were obtained by the reaction of NiCl₂ · 6H₂O and NH₄Cl with aqueous NH₃ solution. The structures of the isotypic compounds (Fm3 m, Z = 4) were determined from single crystal diffractometer data (see “Inhaltsübersicht”). All compounds crystallize in the K₂[PtCl₆] structure type. In these compounds the metal ions have high-spin configuration. The orientation of the dynamically disordered hydrogen atoms of the ammonia ligands is discussed.     

Über Reaktionen oxygenierter Kobalt(II)-Komplexe. IX. Oxydative Eigenschaften von Tetrakis(äthylendiamin)-μ-peroxo-μ-hydroxo-dikobalt(III)

Reactions of oxygenated cobalt(II) complexes. IX. Oxidative properties of tetrakis(ethylenediamine)-μ-peroxo-μ-hydroxo-dicobalt(III)

1 VIII s. [1].

[(en)₂Co(O₂, OH)Co(en)₂]³⁺ ( a ) reacts with I^? in acidic aqueous solution according to: Co^III(O₂, OH)Co^III + 21^? + 5H⁺ ? 2Co^III + 3H₂O + I₂. Using I^? in excess first order rate constants are obtained which, to a first approximation, are independent of [I^?]. Comparison with kinetic data of deoxygenation of [(en)₂Co(O₂, OH)Co(en)₂]³⁺ under analogous conditions suggests that both reactions have the same rate determining step. The singly bridged species [(en)₂(H₂O)CoO₂Co(H₂O) (en)₂]⁴⁺ is shown to be the reactive intermediate in the iodide oxidation (Schema 2).     

Reactions of Beryllium Halides in Liquid Ammonia: The Tetraammineberyllium Cation [Be(NH3)4]2+, its Hydrolysis Products,and the Action of Be2+ as a Fluoride‐Ion Acceptor

The first structural characterization of the text‐book tetraammineberyllium(II) cation [Be(NH₃)₄]²⁺, obtained in the compounds [Be(NH₃)₄]₂Cl₄ ? 17NH₃ and [Be(NH₃)₄]Cl₂, is reported. Through NMR spectroscopic and quantum chemical studies, its hydrolysis products in liquid ammonia were identified. These are the dinuclear [Be₂(μ‐OH)(NH₃)₆]³⁺ and the cyclic [Be₂(μ‐OH)₂(NH₃)₄]²⁺ and [Be₃(μ‐OH)₃(NH₃)₆]³⁺ cations. The latter species was isolated as the compound [Be₃(μ‐OH)₃(NH₃)₆]Cl₃ ? 7NH₃. NMR analysis of solutions of BeF₂ in liquid ammonia showed that the [BeF₂(NH₃)₂] molecule was the only dissolved species. It acts as a strong fluoride‐ion acceptor and forms the [BeF₃(NH₃)]^? anion in the compound [N₂H₇][BeF₃(NH₃)]. The compounds presented herein were characterized by single‐crystal X‐ray structure analysis, ⁹Be, ¹⁷O, and ¹⁹F NMR, IR, and Raman spectroscopy, deuteration studies, and quantum chemical calculations. The extension of beryllium chemistry to the ammine system shows similarities but also decisive differences to the aquo system.     

A novel chain-like molybdenum phosphate: hydrothermal synthesis,crystal structure and characterization of [NH3(CH2CH2)2NH3]3[NH3(CH2CH2)2NH2]-Na5[Mo6O12(OH)3(PO4)(HPO4)3]2·4H2O

A novel organic/inorganic hybrid molybdenum phosphate, [NH₃(CH₂CH₂)₂NH₃]₃[NH₃(CH₂CH₂)₂NH₂]Na₅-[Mo₆O₁₂(OH)₃(PO₄)(HPO₄)₃]₂·4H₂O (1), involving molybdenum presented in V oxidation, has been hydrothermally prepared and characterized by elemental analysis, i.r., u.v.–vis., x.p.s., t.g. and single crystal X-ray diffraction. The structure of the title compound (1) may be considered to consist of two [Mo₆O₁₂(OH)₃(PO₄)(HPO₄)₃] units bonded together with NaO₆ octahedra, forming dimers. Further, these dimers connect with each other through four Na⁺ cations as bridges, giving rise to novel one-dimensional chain-like skeleton. Piperazines exist among inorganic chains acting as charge balancing cations.     

Über Reaktionen oxygenierter Kobalt(II)-Chelate. VI. Präparative Darstellung von diastereoisomeren Tetrakis(äthylendiamin)-μ-peroxo-μ-hydroxodikobalt(III)-perchloraten

On Reactions of oxygenated Cobalt(II) Chelates. VI. Preparation of diastereoisomeric tetrakis(ethylenediamine)-μ-peroxo-μl-hydroxo-dicobalt(III) Perchlorates Oxygenation of Co(en)₂²⁺ leads to a mixture of two isomeric forms of [(en)₂Co(O₂, OH)-Co(en)₂] (ClO₄)₃ · H₂O from which the less soluble meso form can be readily crystallized. Further crystallization from the mother liquor yields the racemate ΔΔ/ΔΔ. The pure racemate may be obtained by either of the following methods: (a) By ligand exchange starting from mono bridged [(NH₃)₅CoO₂Co(NH₃)₅] (NO₃)₄ or from doubly bridged [(SCN) (NH₃)₃Co(O₂, OH)Co(NH₃)₃(SCN)] SCN · 2H₂O. (b) By reaction of cis-[Co(en)₂(OH₂)₂]³⁺ with H₂O₂. Reaction (b) proceeds via an intermediate cis-[Co(en)₂(OOH) (OH₂)] (ClO₄)₂ · H₂O which at higher pH reacts with [Co(en)₂(OH) (OH₂)]²⁺ to yield the desired doubly bridged ΔΔ/ΔΔ tetrakis(ethylenediamine)-μ-peroxo-μ-hydroxodikobalt(III)-perchlorate.     

Binary salt of a palladium(II) complex with (phosphonomethyl)phosphonic (medronic) acid comprising `handbell‐like' [Pd{μ‐CH2(PO3)2}]3 units

The asymmetric unit of the title compound, dipotassium bis[hexaaquanickel(II)] tris(μ₂‐methylenediphosphonato)tripalladium(II) hexahydrate, K₂[Ni(H₂O)₆]₂[Pd₃{CH₂(PO₃)₂}₃]·6H₂O, consists of half a {[Pd{CH₂(PO₃)₂}]₃}⁶⁻ anion [one Pd atom (4e) and a methylene C atom (4e) occupy positions on a twofold axis] in a rare `handbell‐like' arrangement, with K⁺ and [Ni(H₂O)₆]²⁺ cations to form the neutral complex, completed by three solvent water molecules. The {[Pd{CH₂(PO₃)₂}]₃}⁶⁻ units exhibit close Pd...Pd separations of 3.0469 (4) Å and are packed via intermolecular C—H...Pd hydrogen bonds. The [KO₉] and [NiO₆] units are assembled into sheets coplanar with (011) and stacked along the [100] direction. Within these sheets there are [K₄Ni₄O₈] and [K₂Ni₂O₄] loops. Successive alternation of the sheets and [Pd{CH₂(PO₃)₂}]₃ units parallel to [001] produces the three‐dimensional packing, which is also supported by a dense network of hydrogen bonds involving the solvent water molecules.     

dh-μ-Carboxilato-e-μ-hydroxo-f-μ-oxo-bis[trichloroantimone(V)] Struktur und spektroskopsiche Untersuchungen

dh-μ-Carboxilato-e-μ-hydroxo-f-μ-oxo-bis[trichloroantimonies(V)] Structure and Spectroscopic Investigations The title compounds can be prepared by reaction of SbCl₅ · H₂O and RCOOH (R ? CF₃, CCl₃, CHCl₂, CH₂Cl, CH₃, CH₃CH₂, (CH₃)₂CH, H) or by reaction of H₅O₂⁺SbCl₆^? and RCO₂SbCl₄ in good yields. ¹H-NMR investigations proove that there is a rapid exchange between the components in the reaction mixture. The vibrational spectra are discussed in view of the CO₂ vibrations and hydrogen bonding. The crystal and molecular structure of dh-μ-Trichloroacetato-e-μ-hydroxo-f-μ-oxo-bis[trichloroantimony(V)] is determined by X-ray analysis.     

Synthesis,Crystal Structure,and Hydrogen Bonding of μ‐Hydroxo‐μ‐peroxo‐bis[bis(ethylenediamine)cobalt(III)] Squarate

Black‐brown needle‐shaped single crystals of [Co₂(en)₄(O₂)(OH)][C₄O₄]_1.5 · 4H₂O (en = ethylenediamine) were prepared in aqueous solution at room temperature [space group P$\bar{1}$ (no.2) with a = 800.20(8), b = 1225.48(7), c = 1403.84(9) pm, α = 100.282(5), β = 94.515(7), and γ = 95.596(6)°]. The Co³⁺ cations [Co(1), Co(2)] are coordinated in an octahedral manner by four nitrogen atoms stemming from the ethylenediamine molecules and two oxygen atoms each from a hydroxo group and a peroxo group, respectively. Both Co³⁺ coordination polyhedra are connected by a common corner and by the peroxo group leading to the dinuclear [(en)₂Co(O₂)(OH)Co(en)₂]³⁺ cation. The squarate dianions, not bonded to Co³⁺, and the [(en)₂Co(O₂)(OH)Co(en)₂]³⁺ cations are linked by hydrogen bonds forming a three‐dimensional supramolecular network containing water molecules. Magnetic measurements revealed a diamagnetic behavior indicating a low‐spin electron configuration of Co³⁺. The UV/Vis spectra show two LMCT bands [π*(O₂^2–) → d_σ*(Co³⁺)] at 274 and 368 nm and the d–d transition (¹A_1g → ¹T_1g) at 542 nm. Thermoanalytical investigations in air show that the compound is stable up to 120 °C. Subsequent decomposition processes to cobalt oxide are finished at 460 °C.     

Solubilities and Gibbs transfer energies of thiolato,sulfenato, sulfinato and tris(ethylenediamine)cobalt(III) complexes,as well as of perchlorate,from acetonitrile into its mixtures with water

Information on the solvation of thiolato complex cations [Co(en)₂(SCH₂COO)]⁺ [Co(en)₂(SCH₂CH(COO)NH₂)]⁺, [Co(en)₂(SCH₂CH₂NH₂)]²⁺, sulfenato complexes [Co(en)₂(SOCH₂COO)]⁺ [Co(en)₂{SOCH₂CH(COO)NH₂}]⁺, [Co(en)₂(SOCH₂CH₂NH₂)]²⁺, the sulfinato [Co(en)₂{SO₂CH₂CH(COO)NH₂}]⁺, [Co(en)₂(SO₂CH₂CH₂NH₂)]²⁺ as well as of [Co(en)₃]³⁺ has been obtained from solubility measurements in MeCN–H₂O mixtures at 298.2 K. The single-ion Gibbs energies of transfer of the Co^III complexes were derived from the solubilities of picrate and perchlorate salts for the full range of MeCN–H₂O mixtures. Single-ion Gibbs energies of transfer for the perchlorate ion are given. The effects of the solvent mixtures were interpreted in the framework of chemical bond formation between the ions and the individual solvent molecules.     

Bis(tetramethylammonium) hexaaquadodeca‐μ‐bromo‐octahedro‐hexatantalum tetrabromide dihydrate

The novel title compound, [(CH₃)₄N]₂[Ta₆Br₁₂(H₂O)₆]Br₄·2H₂O, with a [Ta₆Br₁₂]²⁺ cluster unit, has been prepared and structurally characterized. The compound crystallizes in space group C2/c, with a twofold axis passing through the cluster and the centre of symmetry located between the clusters. The nearest neighbouring cluster units are aligned along the crystallographic c axis, forming a one‐dimensional chain pattern.     

The Cocrystallization of the Cubic [Ta6Br12(H2O)6][CuBr2X2]·10H2O and Triclinic [Ta6Br12(H2O)6]X2·trans‐[Ta6Br12(OH)4(H2O)2]·18H2O (X = Cl,Br, NO3) Phases with the Coexistence of [Ta6Br12]2+ and [Ta6Br12]4+ in the Latter

Cubic [Ta₆Br₁₂(H₂O)₆][CuBr₂X₂]·10H₂O and triclinic [Ta₆Br₁₂(H₂O)₆]X₂·trans‐[Ta₆Br₁₂(OH)₄(H₂O)₂]·18H₂O (X = Cl, Br, NO₃) cocrystallize in aqueous solutions of [Ta₆Br₁₂]²⁺ in the presence of Cu²⁺ ions. The crystal structures of [Ta₆Br₁₂(H₂O)₆]Cl₂·trans‐[Ta₆Br₁₂(OH)₄(H₂O)₂]·18H₂O ( 1 ) and [Ta₆Br₁₂(H₂O)₆]Br₂·trans‐[Ta₆Br₁₂(OH)₄(H₂O)₂]·18H₂O ( 3 )have been solved in the triclinic space group P&1macr; (No. 2). Crystal data: 1 , a = 9.3264(2) Å, b = 9.8272(2) Å, c = 19.0158(4) Å, α = 80.931(1)?, β = 81.772(2)?, γ = 80.691(1)?; 3 , a = 9.3399(2) Å, b = 9.8796(2) Å, c = 19.0494(4) Å; α = 81.037(1)?, β = 81.808(1)?, γ = 80.736(1)?. 1 and 3 consist of two octahedral differently charged cluster entities, [Ta₆Br₁₂]²⁺ in the [Ta₆Br₁₂(H₂O)₆]²⁺ cation and [Ta₆Br₁₂]⁴⁺ in trans‐[Ta₆Br₁₂(OH)₄(H₂O)₂]. Average bond distances in the [Ta₆Br₁₂(H₂O)₆]²⁺ cations: 1 , Ta‐Ta, 2.9243 Å; Ta‐Brⁱ , 2.607 Å; Ta‐O, 2.23 Å; 3 , Ta‐Ta, 2.9162 Å; Ta‐Brⁱ , 2.603 Å; Ta‐O, 2.24 Å. Average bond distances in trans‐[Ta₆‐Br₁₂(OH)₄(H₂O)₂]: 1 , Ta‐Ta, 3.0133 Å; Ta‐Brⁱ, 2.586 Å; Ta‐O(OH), 2.14 Å; Ta‐O(H₂O), 2.258(9) Å; 3 , Ta‐Ta, 3.0113 Å; Ta‐Brⁱ, 2.580 Å; Ta‐O(OH), 2.11 Å; Ta‐O(H₂O), 2.23(1) Å. The crystal packing results in short O···O contacts along the c axes. Under the same experimental conditions, [Ta₆Cl₁₂]²⁺ oxidized to [Ta₆Cl₁₂]⁴⁺ , whereas [Nb₆X₁₂]²⁺ clusters were not affected by the Cu²⁺ ion.     

Cobalt(II) and Cobalt(III) Tri‐tert‐butoxysilanethiolates. Synthesis,Properties, Crystal and Molecular Structures of [Co{μ‐SSi(OBut)3}{SSi(OBut)3}(NH3)]2 and [Co{SSi(OBut)3}2(NH3)4][SSi(OBut)3] Complexes

The heteroleptic neutral tri‐tert‐butoxysilanethiolate of cobalt(II) incorporating ammonia as additional ligand ( 1 ) has been prepared by the reaction of a cobalt(II) ammine complex with tri‐tert‐butoxysilanethiol in water. Complex 1 , dissolved in hexane, undergoes oxidation in an ammonia saturated atmosphere to the ionic cobalt(III) compound 2 . Molecular and crystal structures of 1 and 2 have been determined by single crystal X‐ray structural analysis. 1 forms a dimeric molecule [Co{μ‐SSi(OBu^t)₃}{SSi(OBu^t)₃}(NH₃)]₂ with a folded central Co₂S₂ ring and distorted tetrahedral ligand arrangement at both Co^II atoms (CoNS₃ core). The product 2 is composed of the octahedral Co^III complex cation [Co{SSi(OBu^t)₃}₂(NH₃)₄]⁺ and the tri‐tert‐butoxysilanethiolate anion. Within the crystal two pairs of ions interact by hydrogen bonds forming well separated entities. 1 and 2 are the first structurally characterized cobalt thiolates where metal is also bonded to ammonia and 2 is the first cobalt(III) silanethiolate.     

Thermolyse von Cyanokomplexen. VII. Über die Thermischen Zersetzungsreaktionen der Hexacyanokobalte(III); Ligandenumlagerungen bei der Thermolyse

Thermolysis of cyano complexes. VII. On the thermal decomposition of hexacyanocobaltate(III); ligand exchange during thermolysis The thermal decomposition of hexacyanocobaltates(III) yields, as products of successive intramolecular redox reactions, first dicyan and Co^II(Co^III)-complexes, then Co^II[Co^II]-complexes and simple Co^II(CN)₂, respectively, and finally Co^ICN and elemental Co, respectively. All the compounds of the [Co^III(NH₃)₆]³⁺ cation with the cyanometallate anions of Co, Fe, Cr, Mn, Ni, Mo yield the same DTA curve as [Co(NH₃)₆][Co(CN)₆] does; in the case of Ni and Cr, which are capable of forming ammine complexes, simultaneous mutual ligand exchange occurs.