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 journalArticle

25 Citations (Scopus)

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
Externally publishedYes

Fingerprint

Nitriles
nitriles
hydrolysis
Hydrolysis
4-nitrobenzonitrile
reactivity
Ionic strength
Osmolar Concentration
Rate constants
Electron transitions
Isomers
carbon 13
Ground state
Carbon
Nuclear magnetic resonance
Kinetics
isomers
plots
slopes
nuclear magnetic resonance

ASJC Scopus subject areas

  • Biochemistry
  • Inorganic Chemistry
  • Physical and Theoretical Chemistry
  • Materials Chemistry

Cite this

Reactivity patterns in the base hydrolysis of coordinated aromatic nitriles. / de la Vega, Ramón López; Ellis, Walther R; Purcell, William L.

In: Inorganica Chimica Acta, Vol. 68, No. C, 1983, p. 97-101.

Research output: Contribution to journalArticle

de la Vega, Ramón López ; Ellis, Walther R ; Purcell, William L. / Reactivity patterns in the base hydrolysis of coordinated aromatic nitriles. In: Inorganica Chimica Acta. 1983 ; Vol. 68, No. C. pp. 97-101.
@article{f62da8e2fadd4e628ab7b76ad2d43db2,
title = "Reactivity patterns in the base hydrolysis of coordinated aromatic nitriles",
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.",
author = "{de la Vega}, {Ram{\'o}n L{\'o}pez} and Ellis, {Walther R} and Purcell, {William L.}",
year = "1983",
doi = "10.1016/S0020-1693(00)88944-6",
language = "English (US)",
volume = "68",
pages = "97--101",
journal = "Inorganica Chimica Acta",
issn = "0020-1693",
publisher = "Elsevier BV",
number = "C",

}

TY - JOUR

T1 - Reactivity patterns in the base hydrolysis of coordinated aromatic nitriles

AU - de la Vega, Ramón López

AU - Ellis, Walther R

AU - Purcell, William L.

PY - 1983

Y1 - 1983

N2 - 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.

AB - 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.

UR - http://www.scopus.com/inward/record.url?scp=0011797095&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0011797095&partnerID=8YFLogxK

U2 - 10.1016/S0020-1693(00)88944-6

DO - 10.1016/S0020-1693(00)88944-6

M3 - Article

AN - SCOPUS:0011797095

VL - 68

SP - 97

EP - 101

JO - Inorganica Chimica Acta

JF - Inorganica Chimica Acta

SN - 0020-1693

IS - C

ER -