INFIQC 05475
INSTITUTO DE INVESTIGACIONES EN FISICO- QUIMICA DE CORDOBA
Unidad Ejecutora - UE
artículos
Título:
Effects of the alkyl substituent in the p-donor heteroatom on the kinetic and thermodynamic acidities of Fischer thiocarbene complexes
Autor/es:
MARTIN EDUARDO ZOLOFF MICHOFF; DIEGO MARCELO ANDRADA; ALEJANDRO MANUEL GRANADOS; RITA HOYOS DE ROSSI
Revista:
NEW JOURNAL OF CHEMISTRY
Editorial:
Royal Society of Chemistry
Referencias:
Lugar: Londres; Año: 2008 vol. 32 p. 65 - 72
ISSN:
1144-0546
Resumen:
Rate constants for the proton transfer reaction from Fischer thiocarbene complexes (CO)5MQC(SR1)CH3 (M = Cr or W; R1 = n-butyl, isopropyl, tert-butyl, cyclohexyl) to OH-and various primary and secondary amines were determined in 50% acetonitrile50% water at25 1C. These measurements allowed the determination of the thermodynamic and kinetic aciditiesfor these substrates. The results obtained show that there is a slight effect of the substituent onthe 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.
