INFIQC 05475
INSTITUTO DE INVESTIGACIONES EN FISICO- QUIMICA DE CORDOBA
Unidad Ejecutora - UE
artículos
Título:
119 Effects of the alkyl substituent in the pi-donor heteroatom on the kinetic and thermodynamic acidities of Fischer thiocarbene complexes,
Autor/es:
MARTIN E. ZOLOFF MICHOFF, DIEGO M. ANDRADA, ALEJANDRO M. GRANADOS, AND RITA HOYOS DE ROSSI
Revista:
NEW JOURNAL OF CHEMISTRY
Referencias:
Año: 2007
ISSN:
1144-0546
Resumen:
Rate constants for the proton transfer reaction from Fischer thiocarbene complexes (CO)5M=C(SR1)CH3 (M = Cr or W; R1 = n-butyl, i-propyl, t-butyl, cyclohexyl) to OH- and various primary and secondary amines were determined in 50 % Acetonitrile 50 % Water at 25º C. These measurements allowed the determination of the thermodynamic and kinetic acidities for these substrates. The results obtained show that there is a slight effect of the substituent on the thermodynamic acidity, which is governed by its hydrophobicity; whereas the effect on the kinetic acidity is more noticeable and is due to the steric effect of the substituent.
