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Titolo:
Structure and reactivity of (PPh4)(3)[W(CN)(5)O]center dot 7H(2)O. Kinetics and mechanism of the reaction with molecular oxygen
Autore:
Szklarzewicz, J; Matoga, D; Samotus, A; Burgess, J; Fawcett, J; Russell, DR;
Indirizzi:
Jagiellonian Univ, Fac Chem, PL-30060 Krakow, Poland Jagiellonian Univ Krakow Poland PL-30060 c Chem, PL-30060 Krakow, Poland Univ Leicester, Dept Chem, Leicester LE1 7RH, Leics, England Univ Leicester Leicester Leics England LE1 7RH er LE1 7RH, Leics, England
Titolo Testata:
CROATICA CHEMICA ACTA
fascicolo: 3, volume: 74, anno: 2001,
pagine: 529 - 544
SICI:
0011-1643(200108)74:3<529:SARO(D>2.0.ZU;2-O
Fonte:
ISI
Lingua:
ENG
Soggetto:
SUBSTITUTION-REACTIONS; IONS; TRANS-DIOXOTETRACYANOTUNGSTATE(IV); COMPLEXES; LIGANDS; ANIONS;
Keywords:
oxopentacyanotungstate(IV); oxoperoxotetracyanotungstate(VI); reaction with dioxygen; kinetics and mechanism;
Tipo documento:
Article
Natura:
Periodico
Settore Disciplinare:
Physical, Chemical & Earth Sciences
Citazioni:
14
Recensione:
Indirizzi per estratti:
Indirizzo: Samotus, A Jagiellonian Univ, Fac Chem, R Ingardena 3, PL-30060 Krakow, Poland Jagiellonian Univ R Ingardena 3 Krakow Poland PL-30060 Poland
Citazione:
J. Szklarzewicz et al., "Structure and reactivity of (PPh4)(3)[W(CN)(5)O]center dot 7H(2)O. Kinetics and mechanism of the reaction with molecular oxygen", CROAT CHEM, 74(3), 2001, pp. 529-544

Abstract

The (PPh4)(3)[W(CN)(5)O] - 7H(2)O has been synthesised and structurally characterised by X-ray diffraction. In the solid state and in ethanol-acetonemixture, the salt reacts with molecular oxygen giving (PPh4)(2)[W(CN)(4)O(O-2)]. The progress of the solid state reaction was followed by measuring infrared spectra. The integrated intensities of the W=O, O-O and C equivalent toN bands changed with time according to the pseudo first-order kinetics. In solution, the kinetic measurements indicate that the rate law is of theform -d[complex]/dt = k[complex][O-2]. The k value is equal to 5.78 ( +/-0.26) mol(-1) dm(3) s(-1) at 298 K. The activation parameters, DeltaH(doubledagger) (k) and AS(double dagger) (k), are 55 (+/-3) kJ mol(-1) and -46 (+/-8) J K-1 mol(-1), respectively. A reaction mechanism is proposed.

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Documento generato il 05/04/20 alle ore 22:34:39