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Structure and Reactivity of (PPh₄)₃[W(CN)₅O] ⋅ 7H₂O. Kinetics and Mechanism of the Reaction with Molecular Oxygen

Janusz Szklarzewicz ; Faculty of Chemistry, Jagiellonian University, R. Ingardena 3, 30-060 Krakóv, Poland
Dariusz Matoga ; Faculty of Chemistry, Jagiellonian University, R. Ingardena 3, 30-060 Krakóv, Poland
Alina Samotus ; Faculty of Chemistry, Jagiellonian University, R. Ingardena 3, 30-060 Krakóv, Poland
John Burgess ; Department of Chemistry, University of Leicester, Leicester LE1 7RH, UK
John Fawcett ; Department of Chemistry, University of Leicester, Leicester LE1 7RH, UK
David R. Russell ; Department of Chemistry, University of Leicester, Leicester LE1 7RH, UK

Sažetak

The (PPh₄)₃[W(CN)₅O] ⋅ 7H₂O has been synthesised and structurally characterised by X-ray diffraction. In the solid state and in ethanol-acetone mixture, the salt reacts with molecular oxygen giving (PPh₄)₂[W(CN)₄O(O₂)]. The progress of the solid state reaction was followed by measuring infrared spectra. The integrated intensities of the W=O, O−O and C≡N bands changed with time according to the pseudo first-order kinetics. In solution, the kinetic measurements indicate that the rate law is of the form -d[complex]/dt = k[complex][O₂]. The k value is equal to 5.78 (±0.26) mol-1 dm3 s-1 at 298 K. The activation parameters, ΔH‡(k) and ΔS‡(k), are 55 (±3) kJ mol-1 and -46 (±8) J K-1 mol-1, respectively. A reaction mechanism is proposed.

Ključne riječi

Oxopentacyanotungstate(IV); oxoperoxotetracyanotung-state(VI); reaction with dioxygen; kinetics and mechanism

Hrčak ID:

131857

URI

https://hrcak.srce.hr/131857

Datum izdavanja:

1.8.2001.

Posjeta: 710 *