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.
Original language | English (US) |
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Pages (from-to) | 97-101 |
Number of pages | 5 |
Journal | Inorganica Chimica Acta |
Volume | 68 |
Issue number | C |
DOIs | |
State | Published - 1983 |
ASJC Scopus subject areas
- Physical and Theoretical Chemistry
- Inorganic Chemistry
- Materials Chemistry