Reactivity patterns in the base hydrolysis of coordinated aromatic nitriles

Ramón López de la Vega, Walther R. Ellis, William L. Purcell

Research output: Contribution to journalArticlepeer-review

25 Scopus citations

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 languageEnglish (US)
Pages (from-to)97-101
Number of pages5
JournalInorganica Chimica Acta
Volume68
Issue numberC
DOIs
StatePublished - 1983

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

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