Hydrolysis of Fischer carbene complexes. Steric effects of the pi-donor group.
Rate constants for the hydrolysis of Fischer carbenes (CO)5Cr=C(OR)Ph (R = n-propyl, neopentyl, isopropyl, and menthyl) in 50% MeCN-50% water (v/v) at 25 degrees C are reported. The rate constants for the addition of -OH to the carbene carbon are 5.3, 3.7, 0.84, and 0.01 M(-1) s(-1), respectively. These rate constants give linear correlations with the corresponding rate constants for the hydrolysis of esters such as acetate, benzoate, and formiate. The slopes of the plots of the observed rate constants for the carbenes vs the rate constants for the esters are 1.4 and 1.2 for acetate and benzoate, respectively, indicating that the factors that decrease the reactivity of the two types of compounds are similar, but the carbenes show higher sensitivity. The rate constants are well correlated with several steric parameters giving a value of -3.84 for the Charton's psi parameter. The results show that the steric bulkiness of the R group is the main factor determining the reactivity differences for these carbene complexes.
Zoloff Michoff
Martin E
ME
Instituto de Investigaciones Fisicoquímicas de Córdoba, Departamento de Química Organica, Facultad de Ciencias Químicas, Universidad Nacional de Córdoba, Ciudad Universitaria, Córdoba, Argentina.
de Rossi
Rita H
RH
Granados
Alejandro M
AM
D006838:Hydrocarbons / Q000138:chemical synthesis / Q000737:chemistry; D006863:Hydrogen-Ion Concentration; D006868:Hydrolysis; D008697:Methane / Q000031:analogs & derivatives* / Q000138:chemical synthesis / Q000737:chemistry; D015394:Molecular Structure
D006838:Hydrocarbons; C030011:carbene; D008697:Methane