Thermodynamics and high-pressure kinetics of a fast carbon dioxide fixation reaction by a (2,6-pyridinedicarboxamidato-hydroxo)nickel(II) complex

The previously reported carbon dioxide fixation reaction by the planar terminal hydroxide complex [Ni(pyN2(Me2))(OH)](1-) in DMF has been further characterized by determination of the equilibrium constants K(eq)²⁹⁸ = 2.4 ± 0.2 × 10(5) M(-1) and K(eq)²²³ = 1.3 ± 0.1 × 10(7) M(-1), as well as the volu...

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Published in:Dalton transactions : an international journal of inorganic chemistry 2014-04, Vol.43 (14), p.5274-5279
Main Authors: Troeppner, O, Huang, D, Holm, R H, Ivanović-Burmazović, I
Format: Article
Language:English
Subjects:
Activation
Binding
Carbon dioxide
Carbon Dioxide - chemistry
Carbon Sequestration
Coordination Complexes - chemistry
Decarboxylation
Fixation
Hydroxides
Hydroxides - chemistry
Kinetics
Nickel - chemistry
Pressure
Reaction kinetics
Terminals
Thermodynamics
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Summary:The previously reported carbon dioxide fixation reaction by the planar terminal hydroxide complex [Ni(pyN2(Me2))(OH)](1-) in DMF has been further characterized by determination of the equilibrium constants K(eq)²⁹⁸ = 2.4 ± 0.2 × 10(5) M(-1) and K(eq)²²³ = 1.3 ± 0.1 × 10(7) M(-1), as well as the volume of activation for the CO2 binding (ΔV(on)(≠223) = -21 ± 3 cm(3) mol(-1)) and back decarboxylation (ΔV(off)(≠223) = -13 ± 1 cm(3) mol(-1)) by high-pressure kinetics. The data are consistent with an earlier DFT computation, including the probable nature of the transition state, and support designating the reaction as one of the most completely investigated carbon dioxide fixation reactions of any type.
ISSN:1477-9226
1477-9234
DOI:10.1039/c3dt53004c