Synthesis and Crystal Structure of Cd(H2O)2Ni(CN)4 · 4H2O

Ham, William K.; Weakley, Timothy J. R.; Page, Catherine J.

doi:10.1006/jssc.1993.1327

Cited by 18 publications

(15 citation statements)

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“…48 Noticeably, the amount of water molecules in such systems remains a complex problem since it influences the crystal structure (three different phases are known). [42][43][44] However it could be noticed that the non-functionalized material 1 shows a step at about a higher 1.8 H2O per unit, in accordance with the two expected CUS in trans position of the octahedral Ni 2+ ions. All these data clearly indicate that despite the PSM, the functionalized clathrates could efficiently adsorb different species in line with the obtained porous volumes based on nitrogen sorption isotherms (Fig.…”

Section: Adsorption Studiessupporting

confidence: 60%

“…1). [42][43][44] The water molecules occupying the axial coordination sites could be easily removed to generate CUS. [39][40][41] Thus, activation of 1 under vacuum at 130 °C followed by the addition of 2 equivalents of either R, S, or racemic (+/) phenylethylamine (L, Scheme 1) in chloroform affords the formation of light purple solids for R-1, S-1 and light blue solid for (+/)-1, respectively (Fig.…”

Section: Synthesis and Characterizationmentioning

confidence: 99%

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Enantioselective separation under humid conditions by chiral Hofmann clathrates: new opportunities for vintage materials

Mamontova

Trens

Salles

et al. 2019

Inorg. Chem. Front.

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Section: Adsorption Studiessupporting

confidence: 60%

Section: Synthesis and Characterizationmentioning

confidence: 99%

Enantioselective separation under humid conditions by chiral Hofmann clathrates: new opportunities for vintage materials

Mamontova

Trens

Salles

et al. 2019

Inorg. Chem. Front.

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“…Two water ligands complete the coordination of the Co center, and an additional four water molecules are trapped between the metal−cyanide sheets. Our structure includes a more complete model of hydrogens than previous studies of compounds with this structure type. ,, However, a truly definitive hydrogen model must await a better crystal and/or neutron diffraction.…”

Section: Resultsmentioning

confidence: 99%

Autoreduction of Pd−Co and Pt−Co Cyanogels: Exploration of Cyanometalate Coordination Chemistry at Elevated Temperatures

et al. 2008

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Cyanogels are coordination polymers made from the reaction of a chlorometalate and a cyanometalate in aqueous solution, which undergo a sol-gel transition to form stable gels. At temperatures above 240 degrees C, the cyanide ligand acts as a reducing agent and reduces the metal centers to lower oxidation states. To understand the mechanism of the autoreduction, the thermal reduction of the Pd-Co cyanogel system formed by the reaction of PdCl4(2-) and Co(CN)6(3-) was studied in an inert atmosphere. It was found that the reduction proceeds through two polymeric cyanide-containing intermediates, CoPd(CN)4 and Pd(CN)2, that form upon reduction of Co(3+) to Co(2+) and involves a significant rearrangement of the coordination structure. The two intermediates upon further heating reduce to metallic products, which by solid-state diffusion form a single Pd/Co alloy product. CoPd(CN)4 was found to have a hydrated form Co(H2O)2Pd(CN)4 x 4 H2O with a layered structure crystallizing in an orthorhombic Pnma space group. The Pt-Co cyanogel was found to autoreduce via a similar route. CoPt(CN)4 was confirmed as an intermediate. Understanding of the mechanism of the cyanogel autoreduction is an important step toward better understanding of opportunities that cyanogels offer in materials chemistry, as well as an expansion of the knowledge of coordination chemistry at elevated temperatures in general.

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“…The mass density of the disk was 1.93 g cm -3 , which is almost the same as the density (1.93 g cm -3 ) determined by single-crystal X-ray diffraction. 13,14 For electrodes, two circular pieces of gold foil with diameter of 10.09 mm was attached with a thin layer of Apiezon N-grease on both sides of the sample disk. The disk was mounted in a double thermostated environment in a cryostat.…”

Section: Methodsmentioning

confidence: 99%

“…The present compound Cd(H 2 O) 2 Ni(CN) 4 ‚4H 2 O, which was synthesized in 1993, 13,14 also has a two-dimensional hydrogenbonded network. The X-ray diffraction study has revealed that this crystal belongs to the space group Pnma (no.…”

Section: Introductionmentioning

confidence: 99%

Calorimetric and Dielectric Studies on the Water Reorientation in the Two-Dimensional Hydrogen-Bond System of Cd(H₂O)₂Ni(CN)₄·4H₂O Crystal

Okishiro¹,

Yamamuro²,

Tsukushi³

et al. 1997

J. Phys. Chem. B

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The heat capacity of Cd(H2O)2Ni(CN)4·4H2O crystal in which the water molecules form a two-dimensional quasi-hexagonal hydrogen-bond network was measured with an adiabatic calorimeter in the temperature range 5−300 K. A glass transition due to the freezing of the reorientational motion of the water molecules was found around 120 K. The reorientational relaxation times were obtained from the enthalpy relaxation data around the glass transition. The complex dielectric permittivity was also measured in the temperature range 150−285 K and in the frequency range 20 Hz−1 MHz. A dielectric dispersion associated with the reorientational motion of the water molecules was observed in the temperature range 160−270 K. The dielectric relaxation times were calculated from the temperature and frequency dependence of the ε‘‘ data. Calorimetric and dielectric relaxation times lie on separate smooth lines in the wide time scale over 10-6−106 s in the Arrhenius plot. The mechanism of the water reorientational motion was discussed on the basis of the model considering the formation and transfer of the Bjerrum defect as in the case of the three-dimensional ice polymorphs.

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Synthesis and Crystal Structure of Cd(H2O)2Ni(CN)4 · 4H2O

Cited by 18 publications

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Enantioselective separation under humid conditions by chiral Hofmann clathrates: new opportunities for vintage materials

Enantioselective separation under humid conditions by chiral Hofmann clathrates: new opportunities for vintage materials

Autoreduction of Pd−Co and Pt−Co Cyanogels: Exploration of Cyanometalate Coordination Chemistry at Elevated Temperatures

Calorimetric and Dielectric Studies on the Water Reorientation in the Two-Dimensional Hydrogen-Bond System of Cd(H₂O)₂Ni(CN)₄·4H₂O Crystal

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Synthesis and Crystal Structure of Cd(H2O)2Ni(CN)4 · 4H2O

Cited by 18 publications

References 0 publications

Enantioselective separation under humid conditions by chiral Hofmann clathrates: new opportunities for vintage materials

Enantioselective separation under humid conditions by chiral Hofmann clathrates: new opportunities for vintage materials

Autoreduction of Pd−Co and Pt−Co Cyanogels: Exploration of Cyanometalate Coordination Chemistry at Elevated Temperatures

Calorimetric and Dielectric Studies on the Water Reorientation in the Two-Dimensional Hydrogen-Bond System of Cd(H2O)2Ni(CN)4·4H2O Crystal

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Calorimetric and Dielectric Studies on the Water Reorientation in the Two-Dimensional Hydrogen-Bond System of Cd(H₂O)₂Ni(CN)₄·4H₂O Crystal