Alkenes (cyclohexene; 1-octene) react with cis-PtCl2(CO)(2), leading to cis-PtCl2(CO)(alkene) (1a, alkene) cyclohexene; 1b, alkene = 1-octene). The substitution kinetics to 1a and 1b in 1,2-dichloroethane in the temperature range 273-308 K have the following second-order rate constants at 298 K, respectively: cyclohexene, (0.94 +/- 0.07) x 10(-3) M-1 s(-1); 1-octene, (2.33 +/- 0.05) x 10(-2) M-1 s(-1). The activation parameters are Delta H* = 37 +/- 4 kJ mol(-1), Delta S* = -180 +/- 10 J K-1 mol(-1) for the reaction affording 1a and Delta H* = 36.5 +/- 0.7 kJ mol(-1), Delta S* = -154 +/- 2 J K-1 mol(-1) for the reaction to 1b. The large negative values of the activation entropies are consistent with an associative mechanism. The reverse reactions proceed with a similar rate constant.

A kinetic study of the competition between carbon monoxide and alkenes in chloro complexes of platinum(II)

BELLI, DANIELA;CALDERAZZO, FAUSTO;CARBONARO, LAURA;LABELLA, LUCA;
2006-01-01

Abstract

Alkenes (cyclohexene; 1-octene) react with cis-PtCl2(CO)(2), leading to cis-PtCl2(CO)(alkene) (1a, alkene) cyclohexene; 1b, alkene = 1-octene). The substitution kinetics to 1a and 1b in 1,2-dichloroethane in the temperature range 273-308 K have the following second-order rate constants at 298 K, respectively: cyclohexene, (0.94 +/- 0.07) x 10(-3) M-1 s(-1); 1-octene, (2.33 +/- 0.05) x 10(-2) M-1 s(-1). The activation parameters are Delta H* = 37 +/- 4 kJ mol(-1), Delta S* = -180 +/- 10 J K-1 mol(-1) for the reaction affording 1a and Delta H* = 36.5 +/- 0.7 kJ mol(-1), Delta S* = -154 +/- 2 J K-1 mol(-1) for the reaction to 1b. The large negative values of the activation entropies are consistent with an associative mechanism. The reverse reactions proceed with a similar rate constant.
Belli, Daniela; Riccardo, Bini; Calderazzo, Fausto; Carbonaro, Laura; Labella, Luca; Anna, Vitullo
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11568/181672
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