Cobalt(II) cyanide and its complexes with water, ammonia and cyanide ions

Mosha, Dms; Nicholls, David

doi:10.1016/s0020-1693(00)91947-9

Cited by 12 publications

(6 citation statements)

References 13 publications

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“…It is possible that the number of coordinated cyanide ligands on Co is decreasing, seen by the shift of the terminal cyanide stretching vibrations, ν(CN) to higher frequency 23 as seen by the three peaks at 2236, 2221, and 2176 cm -1 and in the lowfrequency region decrease of the ν(CoC) stretching vibrations to 458 cm -1 . After the second inflection point (280 °C) a very pronounced peak at 2194 cm -1 is seen in the high-frequency region (Figure 5c) along with the further shift of two peaks in the low-frequency region to 534 and 451 cm -1 which we tentatively ascribe to the stretching vibration and bending modes of cyanide ligands 23,28,29 in Co(CN) n (n < 6). It is also possible that these transitions are due to the to formation of KPdCo-(CN) 6 compounds, or to formation of Pd(CN) 2 formed by the "flipping" of the cyanide bridges [30][31][32][33] to form Co-NC-Pd bridges.…”

Section: Resultsmentioning

confidence: 67%

Use of Sol−Gel Chemistry for the Preparation of Cyanogels as Ceramic and Alloy Precursors

et al. 1996

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The reaction of aqueous solutions of K2PdCl4 and K3Co(CN)6 results in gellike polymeric materials, characterized by bridging cyanides between the central metals of the adducts. These materials tend to be rigid in nature but contain in excess of 95% water by weight. We refer to these novel transition metal based hydrogels as cyanogels. In contrast to classic inorganic hydrogels these materials are not based on an oxide network. Dehydration of the cyanogels results in amorphous xerogels which maintain the initial polymeric structure of the cyanogel. Thermal processing of gels containing palladium and cobalt centers under an inert atmosphere at temperatures between 200 and 500 °C, produces a new metastable material. Sintering between 500 and 1000 °C produces ferromagnetic alloys, while processing under oxygen in the same temperature region gives the ceramic mixed oxide material PbCoO2, having the delafossite structure.

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Section: Resultsmentioning

confidence: 67%

Use of Sol−Gel Chemistry for the Preparation of Cyanogels as Ceramic and Alloy Precursors

et al. 1996

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“…An infrared spectrum of the post-electrolysis solution after solvent removal exhibits a small peak at 2060 cm –1 , a value similar to cobalt cyanide complexes. 45 (see Fig. S11 † ) Another contribution to the decline in activity may be an increase in solution acidity during electrolysis that promotes decomposition by ligand deprotonation.…”

Section: Resultsmentioning

confidence: 99%

Intramolecular hydrogen-bonding in a cobalt aqua complex and electrochemical water oxidation activity

et al. 2018

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“…Earlier [Co(CN) 4 ] 2 - Systems. Prior to this study, only three tetracyanocobaltate(II) complexes had been isolated in the solid state: monomeric (PNP) 2 Co(CN) 4 · 4DMF and (PNP) 2 Co(CN) 4 (PNP is the bis(triphenylphosphine)nitrogen(1+)) and polymeric K 2 Co(CN) 4 …”

Section: Resultsmentioning

confidence: 99%

Tetrabutylammonium Tetracyanocobaltate(II) Dioxygen Carriers

et al. 1997

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The second example of a low-spin, square-planar Co(II)L(4) species (L = unidentate ligand), (Bu(4)N)(2)Co(CN)(4) (1), and a new family of tetrabutylammonium tetracyanocobaltate(II) complexes have been isolated and characterized. All of the solid compounds react reversibly with dioxygen to form 1:1 cobalt(III)-superoxo complexes. Since a variety of neutral bases react readily with 1 and the complexes can be obtained as solids, the effects of different axial bases on the dioxygen-binding behavior of the solids could also be studied. Interestingly, reversible phase changes occur on oxygenation/deoxygenation for (Bu(4)N)(2)[Co(CN)(4).C(5)H(5)N] (2) and [(Bu(4)N)(2)Co(CN)(4)](2).(C(10)H(8)N(2)) (3). Presumably this happens because the crystal lattices of the unoxygenated materials do not contain enough room for the dioxygen. Complex 2 crystallizes in the orthorhombic space group Pbcm with the following cell parameters at 25 degrees C: a = 9.024(3) Å, b = 21.886(8) Å, c = 23.184(6) Å, V = 4578.6(27) Å(3), and Z = 4. From the molecular packing, it is apparent that the [Co(CN)(4).C(5)H(5)N](2)(-) anions are aligned parallel to the a axis, with the pyridine of each anionic unit pointing toward the vacant site on the cobalt of the adjacent anion. The tetrabutylammonium cations completely surround the anions, forming hydrophobic casings that also run parallel to the a axis. Thus, it is clear that the bulky tetrabutylammonium cations are capable of separating the cobalt centers so that &mgr;-peroxo dimers cannot form.

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Cobalt(II) cyanide and its complexes with water, ammonia and cyanide ions

Cited by 12 publications

References 13 publications

Use of Sol−Gel Chemistry for the Preparation of Cyanogels as Ceramic and Alloy Precursors

Use of Sol−Gel Chemistry for the Preparation of Cyanogels as Ceramic and Alloy Precursors

Intramolecular hydrogen-bonding in a cobalt aqua complex and electrochemical water oxidation activity

Tetrabutylammonium Tetracyanocobaltate(II) Dioxygen Carriers

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