A hemocyanic model compound, copper complex with 1, 3-bis(2-benzoimidazolylmethyl)aminomethyl] cyclohexane

The syntheses of several novel copper-() and -() compounds containing triazacyclohexanes with one or three 2-pyridylmethyl substituents are described. The molecular structures of (2-PyMe) 3 TACCuCl 2 3, [(2-PyMe)Et 2 -TACCuCl 2 ] 2 4 and [(2-PyMe) 3 TACCu I ](BF 4 ) 5 have been determined by single crystal X-ray diffraction. The reactivity of 5 and [(2-PyMe)Et 2 TACCu](BF 4 ) 7 towards dioxygen was investigated and a very stable oxidation product with a Cu 4 (OH) 4 cubane core could be obtained in high yield simply by exposing 7 to the atmosphere.

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“…using the ligand Cyb. 7 A common feature in many of these ligands is the 2-pyridylmethylamine motif.…”

Section: Introductionmentioning

confidence: 99%

Coordination chemistry of copper-(i) and -(ii) with 2-pyridylmethyl substituted triazacyclohexanes

et al. 2003

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“…These reactions have not received complete acceptance;10 the pertinent literature has been reviewed by Zambonin11 and Burke and Kerridge.12 Like the nitrate ion, the nitite ion has been treated as a Lux-Flood base. The dissociation of the nitrite ion has been postulated to occur with the formation of the nitrosonium ion and oxide N02 Ft NO+ + O2- (7) As in the case of the nitronium ion, the nitrosonium cation has not been directly observed. Its existence has been inferred from emf measurements and an equilibrium constant determined.…”

Section: Introductionmentioning

confidence: 99%

“…1970, 6, 333 significantly larger than that for reaction 2 (1 X 10-9 vs. 6 X 10-24 at 300 °C),9 reaction 7 could be considered to be a significant source of oxide ion. If we assume that the heat of reaction for reaction 7 is the same as that for reaction 2 and use the equilibrium value of the concentration of the nitrite ion at 600 °C (vide infra), the oxide ion concentration resulting from reaction 7 is found to be ~10-8 mol/kg. Consequently, it appears that neither reaction 2 nor reaction 7 is significant at temperatures between 500 and 600 °C.…”

Section: Introductionmentioning

confidence: 99%

Nitrate/nitrite chemistry in sodium nitrate-potassium nitrate melts

Nissen¹,

Meeker²

1983

Inorg. Chem.

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By chemical analysis of samples taken under carefully controlled conditions, we have been able to show that the only reaction of any consequence that takes place in the equimolar binary NaN03-KN03 system over the temperature range °C is represented by N03~< =* N02~+ V202. Over this temperature range there is no evidence of the formation of any anionic oxygen species such as oxide, peroxide, or superoxide at concentrations greater than 10~5 mol/kg. Equilibrium constants for the above reaction have been determined over the temperature range 500-600 °C. The standard free energy for this reaction [ °(keal/mol) = 23 000 + 20.6 T) has been derived from the experimental data and is in good agreement with similar results for the single salts. A study of the kinetics of the oxidation of nitrite showed the rate of that reaction to be overall second order, first order with respect to both nitrite and oxygen. The rate constants have been measured from 400 to 500 °C, and from their temperature dependence the activation energy for the oxidation of nitrite was calculated: 26.4 kcal/mol.

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