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Kinetics of the metal exchange in Bis(salicylaldiminato)-copper(II)-complexes. Pt. 3. Influence of the electron density at the donor nitrogen

Journal Article:

Abstract

The kinetics of isotopic copper exchange between various (bis-(N-phenyl-salicylaldiminato))copper(II)complexes (= CuL/sub 2/) and mono(pyridine)copper(II)acetate (= CuAc/sub 2/py) was studied in dichloromethane as solvent in the temperature range -20 to +20/sup 0/C. The exchange follows the experimental rate law (5), which is simplified in certain cases due to k''((CuAc/sub 2/py)/sub 2/)/sup 1///sup 2/ < 1. The variation of substituents X on the salicylaldehyde ring and of substituents Y on the N-phenyl ring leads via Hammett plots to the conclusion that substituent effects become apparent as rate increasing or rate decreasing only in those cases, in which they cause an increase or decrease in electron density at the donor oxygen. Substituents Y in 2-position, and especially in 2.6-position, reduce the rate of exchange with increasing van der Waals radius of Y. The mechanistic implications of the results are discussed. (orig.) 891 HK.
Authors:
Winkler, H; Wannowius, K J; Elias, H [1] 
  1. Technische Hochschule Darmstadt (Germany, F.R.). Fachbereich Anorganische Chemie und Kernchemie
Publication Date:
Jan 01, 1977
Product Type:
Journal Article
Reference Number:
AIX-10-429503; EDB-79-078666
Resource Relation:
Journal Name: Z. Phys. Chem. (Frankfurt); (Germany, Federal Republic of); Journal Volume: 107:1
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; COPPER 64; ISOTOPIC EXCHANGE; ACETATES; CHEMICAL REACTION KINETICS; COPPER COMPLEXES; ELECTRON DENSITY; LIGANDS; ORGANIC SOLVENTS; ORGANOMETALLIC COMPOUNDS; PYRIDINES; SALICYLIC ACID; STEREOCHEMISTRY; AZINES; BETA DECAY RADIOISOTOPES; BETA-MINUS DECAY RADIOISOTOPES; BETA-PLUS DECAY RADIOISOTOPES; CARBOXYLIC ACID SALTS; CARBOXYLIC ACIDS; COMPLEXES; COPPER ISOTOPES; ELECTRON CAPTURE RADIOISOTOPES; HETEROCYCLIC COMPOUNDS; HOURS LIVING RADIOISOTOPES; HYDROXY ACIDS; INTERMEDIATE MASS NUCLEI; ISOTOPES; KINETICS; NUCLEI; ODD-ODD NUCLEI; ORGANIC ACIDS; ORGANIC COMPOUNDS; ORGANIC NITROGEN COMPOUNDS; RADIOISOTOPES; REACTION KINETICS; SOLVENTS; TRANSITION ELEMENT COMPLEXES; 400303* - Organic Chemistry- Isotope Exchange & Isotope Separation- (-1987)
OSTI ID:
6267806
Country of Origin:
Germany
Language:
German
Other Identifying Numbers:
Journal ID: CODEN: ZPCFA
Submitting Site:
INIS
Size:
Pages: 57-76
Announcement Date:

Journal Article:

Citation Formats

Winkler, H, Wannowius, K J, and Elias, H. Kinetics of the metal exchange in Bis(salicylaldiminato)-copper(II)-complexes. Pt. 3. Influence of the electron density at the donor nitrogen. Germany: N. p., 1977. Web.
Winkler, H, Wannowius, K J, & Elias, H. Kinetics of the metal exchange in Bis(salicylaldiminato)-copper(II)-complexes. Pt. 3. Influence of the electron density at the donor nitrogen. Germany.
Winkler, H, Wannowius, K J, and Elias, H. 1977. "Kinetics of the metal exchange in Bis(salicylaldiminato)-copper(II)-complexes. Pt. 3. Influence of the electron density at the donor nitrogen." Germany.
@misc{etde_6267806,
title = {Kinetics of the metal exchange in Bis(salicylaldiminato)-copper(II)-complexes. Pt. 3. Influence of the electron density at the donor nitrogen}
author = {Winkler, H, Wannowius, K J, and Elias, H}
abstractNote = {The kinetics of isotopic copper exchange between various (bis-(N-phenyl-salicylaldiminato))copper(II)complexes (= CuL/sub 2/) and mono(pyridine)copper(II)acetate (= CuAc/sub 2/py) was studied in dichloromethane as solvent in the temperature range -20 to +20/sup 0/C. The exchange follows the experimental rate law (5), which is simplified in certain cases due to k''((CuAc/sub 2/py)/sub 2/)/sup 1///sup 2/ < 1. The variation of substituents X on the salicylaldehyde ring and of substituents Y on the N-phenyl ring leads via Hammett plots to the conclusion that substituent effects become apparent as rate increasing or rate decreasing only in those cases, in which they cause an increase or decrease in electron density at the donor oxygen. Substituents Y in 2-position, and especially in 2.6-position, reduce the rate of exchange with increasing van der Waals radius of Y. The mechanistic implications of the results are discussed. (orig.) 891 HK.}
journal = {Z. Phys. Chem. (Frankfurt); (Germany, Federal Republic of)}
volume = {107:1}
journal type = {AC}
place = {Germany}
year = {1977}
month = {Jan}
}