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Title: Organochromium(III) complexes derived from nitriles

Abstract

Reactions of chromium(II) perchlorate with acidified solutions of hydrogen peroxide in water containing modest concentrations of an organic nitrile (RCN) give rise to the cationic organochromium complexes CrCH/sub 2/CN/sup 2 +/ (RCN = acetonitrile), CrCH/sub 2/CH/sub 2/CN/sup 2 +/ (propionitrile), and CrCH/sub 2/CH(CH/sub 3/)CN/sup 2 +/ (isobutyronitrile). These cyanoalkyl complexes are quite resistant to decomposition in aqueous perchloric acid and can be separated by ion-exchange chromatography. Their composition was established by identification of the organic bromide formed by reaction with aqueous bromine. The complexes react with Hg/sup 2 +/ first to form the corresponding HgR/sup +/ and then (if excess organochromium is present) HgR/sub 2/. Kinetic studies for the first stage of this reaction were carried out. The data are consistent with a bimolecular electrophilic substitution process (S/sub E/2 mechanism).

Authors:
;
Publication Date:
OSTI Identifier:
6418080
DOE Contract Number:  
W-7405-ENG-82
Resource Type:
Journal Article
Journal Name:
Inorg. Chem.; (United States)
Additional Journal Information:
Journal Volume: 20:3
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; CHROMIUM COMPLEXES; CHEMICAL PREPARATION; CHEMICAL REACTIONS; MERCURY COMPOUNDS; NITRILES; ORGANOMETALLIC COMPOUNDS; HYDROGEN PEROXIDE; COMPLEXES; HYDROGEN COMPOUNDS; ORGANIC COMPOUNDS; ORGANIC NITROGEN COMPOUNDS; OXYGEN COMPOUNDS; PEROXIDES; SYNTHESIS; TRANSITION ELEMENT COMPLEXES; 400301* - Organic Chemistry- Chemical & Physicochemical Properties- (-1987); 400201 - Chemical & Physicochemical Properties

Citation Formats

Funke, L A, and Espenson, J H. Organochromium(III) complexes derived from nitriles. United States: N. p., 1981. Web. doi:10.1021/ic50217a050.
Funke, L A, & Espenson, J H. Organochromium(III) complexes derived from nitriles. United States. https://doi.org/10.1021/ic50217a050
Funke, L A, and Espenson, J H. Sun . "Organochromium(III) complexes derived from nitriles". United States. https://doi.org/10.1021/ic50217a050.
@article{osti_6418080,
title = {Organochromium(III) complexes derived from nitriles},
author = {Funke, L A and Espenson, J H},
abstractNote = {Reactions of chromium(II) perchlorate with acidified solutions of hydrogen peroxide in water containing modest concentrations of an organic nitrile (RCN) give rise to the cationic organochromium complexes CrCH/sub 2/CN/sup 2 +/ (RCN = acetonitrile), CrCH/sub 2/CH/sub 2/CN/sup 2 +/ (propionitrile), and CrCH/sub 2/CH(CH/sub 3/)CN/sup 2 +/ (isobutyronitrile). These cyanoalkyl complexes are quite resistant to decomposition in aqueous perchloric acid and can be separated by ion-exchange chromatography. Their composition was established by identification of the organic bromide formed by reaction with aqueous bromine. The complexes react with Hg/sup 2 +/ first to form the corresponding HgR/sup +/ and then (if excess organochromium is present) HgR/sub 2/. Kinetic studies for the first stage of this reaction were carried out. The data are consistent with a bimolecular electrophilic substitution process (S/sub E/2 mechanism).},
doi = {10.1021/ic50217a050},
url = {https://www.osti.gov/biblio/6418080}, journal = {Inorg. Chem.; (United States)},
number = ,
volume = 20:3,
place = {United States},
year = {1981},
month = {3}
}