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Kinetics and mechanism of the substitution of olefinic ligands by triphenylantimony in (π‐monoolefin) tetracarbonyliron complexes
Author(s) -
Cardaci G.
Publication year - 1973
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.550050508
Subject(s) - chemistry , substituent , toluene , kinetics , olefin fiber , ligand (biochemistry) , substitution reaction , medicinal chemistry , mechanism (biology) , photochemistry , reaction mechanism , stereochemistry , organic chemistry , catalysis , receptor , biochemistry , physics , philosophy , epistemology , quantum mechanics
The kinetics of the reaction\documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm Fe}\left( {{\rm CO}} \right)_4 \left( {{\rm CH}_2{{=\!=}} {\rm CHX}} \right) + {\rm SbPh}_3 \to {\rm Fe}\left( {{\rm CO}} \right)_4 {\rm SbPh}_3 + {\rm CH}_2{{=\!=}}{\rm CHX}$$\end{document}\documentclass{article}\pagestyle{empty}\begin{document}$$ \left( {{\rm X} = {\rm OEt},{\rm Ph},{\rm Bu}^n ,{\rm Cl},{\rm Br},{\rm CO}_2 {\rm Me},{\rm CN}} \right) $$\end{document}have been studied in toluene solution. The reaction occurs by a dissociative mechanism and the observation of an appreciable mass law retardation effect shows that Fe(CO) 4 is produced as an intermediate. Analysis of the effect of the substituent X on the stability of the complexes leads to the conclusion that π‐backbonding between the metal and the olefinic ligand is the major cause of the M‐olefin bond strength.