Structure of iron (II) and cobalt (II) bromide complexes in aqueous solution by X-ray diffraction analysis

Structures of bromo-metal complexes in concentrated aqueous solutions of FeBr₂ and of CoBr₂ were investigated by X-ray diffraction analysis. The complexes possess an octahedral geometry coordinating Br^– along with H₂O ligands. The frequency factors of metal-Br contacts per one atom of metal were 0.325 for the 2.7M (mol-dm^–3) and 0.747 for the 4.5M FeBr₂ solutions, and 0.280 for the 2.8M and 0.595 for the 4.3M CoBr₂ solutions. The frequency factors suggested that the tendency of metal ions to forming monobromo complexes is in the order, Fe>Co>Ni相似文献   

Tetrachlorobis(N1-phenylacet­amidino-κN2)rhenium(IV) at 11 K by X-­ray diffraction and at 20 K by neutron diffraction

The crystal structure of the title compound, [ReCl₄(C₈H₁₀N₂)₂], has been determined by X-ray diffraction at 11 K and by neutron diffraction at 20 K. The accurate and extensive data sets lead to more precise determinations than are available from earlier work. The agreement in atomic positional and displacement parameters at these very low temperatures is good. The results will facilitate re-examination of the magnetic structure of the complex. The Re atom lies on a special position and the molecule has twofold crystallographic symmetry.     

Reactions of salts of hexakis(pyridine N-oxide)M(II) complexes (M = Co,Ni, Zn) and alkali halides used in infrared spectroscopy

A number of salts of hexakis(pyridine N-oxide)zinc(II) complexes decompose in alkali halide pellets. Initially ion exchange occurs, often followed by the formation of Zn(pyno)₃X₂ (pyno = pyridine N-oxide; X = Br, Cl). The analogous cobalt and nickel compounds are nearly always stable. A mull between alkali halide plates gives greater amounts of the same product Washing this product with toluene gives Zn(pyno)₂X₂. Examples of i.r. and far i.r. spectra are given. Energetical and structural effects are discussed. Far i.r. spectra of M(pyno)₃X₂(M = Co, Zn) confirm the structure [M(pyno)₆][MX₄] for these compounds. New compounds are [Zn(pyno)₂(NO₃)₂], [Zn(pyno-d₅)₂[NO₃)₂], [Zn(pyno-d₅)₆](NO₃)₂ and [Zn(pyno)₆]I₂.     

Gaseous complexes of cobalt(II) bromide and pyridine

The stepwise decomposition of CoBr₂py₂(s) has been investigated on a thermobalance by the “modified entrainment” method yielding Δ₁H=88.6 kJ mol¹, Δ₁S=156.6 JK^?1 mol^?1 and Δ₂H=119.0 kJ mol^?1, Δ₂S=211.8 JK^?1 mol^?1 for the dissociation of the first and second pyridine. The evaporation of CoBr₂py₂(l) and the association of gaseous pyridine to CoBr₂py(l) forming CoBr₂py₂(g) has been studied by vis spectroscopy at 250?420°C. By combining the new results with literature values, a complete thermodynamic cycle for the solid-liquid-gas equilibria in the CoBr₂-pyridine system could be established. It shows that in solution the formation of CoBr₂py₂ is not determined by the cobalt-pyridine bond energy but by the solvation energy of the rectants.     

Organic amines reduce trans-dichlorotetrakis(pyridine)cobalt(III) chloride to cobalt(II)

Summary The reaction of dichlorotetrakis(pyridine)cobalt(III) chloride. [CoCl₂(Py)₄]Cl, with alkyl- or arylamines in EtOH or i-PrOH yielded [CoCl₂(Py)₂] in all cases. This reduction of Co^III to Co^II takes place only in the presence of the amines. [CoCl₂(Py)₂] in EtOH is oxidized by Cl₂ gas and in the presence of pyridine gives [CoCl₂(Py)₄] ⁺, while in pyridine alone [CoCl₂(Py)₄] is formed.