Reactivity patterns in the base hydrolysis of coordinated aromatic nitriles Article

de la Vega, RL, Ellis, WR, Purcell, WL. (1983). Reactivity patterns in the base hydrolysis of coordinated aromatic nitriles . INORGANICA CHIMICA ACTA, 68(C), 97-101. 10.1016/S0020-1693(00)88944-6

cited authors

  • de la Vega, RL; Ellis, WR; Purcell, WL

authors

abstract

  • Two new aromatic organonitrile complexes of pentaamminecobalt(III) have been synthesized, the complexes of 2- and 4-nitrobenzonitrile. The kinetics of their base hydrolysis to coordinated carboxamides have been measured and found to follow a simple second order rate law with rate constants of 180 ± 4 M-1 s-1 and 510 ± 90 M-1 s-1 at 25°C and ionic strength 1.0 for the ortho and para isomers respectively. Rate constants for the hydrolysis of eleven coordinated substituted aromatic nitriles have been found to follow a Hammett type correlation where log k = 1.93σ + 1.30 at 25 °C and ionic strength 1. Carbon-13 NMR studies indicate that the variation in the slope of these Hammett plots for free and coordinated nitrile hydrolysis rates is a transition state effect rather than a ground state phenomenon. © 1983.

publication date

  • January 1, 1983

published in

Digital Object Identifier (DOI)

start page

  • 97

end page

  • 101

volume

  • 68

issue

  • C