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Interest of uranium complexes for the mechanism study of the McMurry reaction; Interet des complexes de l`uranium pour l`etude du mecanisme de la reaction de McMurry

Abstract

The reducing coupling reactions of ketones in diols and olefins are generally carried out with titanium or samarium compounds. In this work uranium complexes have been used. They have allowed to study the chemical reaction mechanism. This thesis is divided into three parts: 1) the reduction mechanism of uranium tetrachloride by cyclic voltametry has been studied at first. It has been shown that this reduction is followed by a transfer reaction of chlorides between the reduced specie of the higher electronic density and UCl . 2) In the second part is described: the synthesis, the crystal structure, the reactivity of the chemical agents, the stereochemistry of diols and alkenes formation and the pinacolisation reaction catalysis. 3) In the last part, the limits of the McMurry reaction are given by the study of the aromatic ketones pinacolisation reaction by-products. The obtained results show that the complexes of the metals which present a high reducing and oxo-philic (Ti, Sm, U..) character react in a similar way with the carbonyl compounds. If the uranium compounds are less used than those of the titanium in the field of the organic synthesis applications, they are precious auxiliaries and excellent models for reactions mechanisms study and  More>>
Authors:
Publication Date:
Jul 04, 1997
Product Type:
Thesis/Dissertation
Report Number:
FRCEA-TH-617
Reference Number:
SCA: 400201; PA: AIX-30:003785; EDB-99:025561; SN: 99002059698
Resource Relation:
Other Information: DN: 284 refs.; TH: These (D. es Sc.); PBD: 4 Jul 1997
Subject:
40 CHEMISTRY; ALKENES; BENCH-SCALE EXPERIMENTS; CATALYSTS; CHEMICAL PREPARATION; CHEMICAL REACTION KINETICS; GLYCOLS; KETONES; NUCLEAR MAGNETIC RESONANCE; OPTIMIZATION; REDUCTION; SAMARIUM COMPLEXES; STEREOCHEMISTRY; TITANIUM CHLORIDES; TITANIUM COMPLEXES; URANIUM CHLORIDES; URANIUM COMPLEXES; VOLTAMETRY
OSTI ID:
313034
Research Organizations:
CEA Saclay, 91 - Gif-sur-Yvette (France). Lab. de Chimie de l`Uranium; Universite Pierre et Marie Curie, 75 - Paris (France)
Country of Origin:
France
Language:
French
Other Identifying Numbers:
Other: ON: DE99612411; TRN: FR9802617003785
Availability:
INIS; OSTI as DE99612411
Submitting Site:
FRN
Size:
249 p.
Announcement Date:
Mar 10, 1999

Citation Formats

Maury, O. Interest of uranium complexes for the mechanism study of the McMurry reaction; Interet des complexes de l`uranium pour l`etude du mecanisme de la reaction de McMurry. France: N. p., 1997. Web.
Maury, O. Interest of uranium complexes for the mechanism study of the McMurry reaction; Interet des complexes de l`uranium pour l`etude du mecanisme de la reaction de McMurry. France.
Maury, O. 1997. "Interest of uranium complexes for the mechanism study of the McMurry reaction; Interet des complexes de l`uranium pour l`etude du mecanisme de la reaction de McMurry." France.
@misc{etde_313034,
title = {Interest of uranium complexes for the mechanism study of the McMurry reaction; Interet des complexes de l`uranium pour l`etude du mecanisme de la reaction de McMurry}
author = {Maury, O}
abstractNote = {The reducing coupling reactions of ketones in diols and olefins are generally carried out with titanium or samarium compounds. In this work uranium complexes have been used. They have allowed to study the chemical reaction mechanism. This thesis is divided into three parts: 1) the reduction mechanism of uranium tetrachloride by cyclic voltametry has been studied at first. It has been shown that this reduction is followed by a transfer reaction of chlorides between the reduced specie of the higher electronic density and UCl . 2) In the second part is described: the synthesis, the crystal structure, the reactivity of the chemical agents, the stereochemistry of diols and alkenes formation and the pinacolisation reaction catalysis. 3) In the last part, the limits of the McMurry reaction are given by the study of the aromatic ketones pinacolisation reaction by-products. The obtained results show that the complexes of the metals which present a high reducing and oxo-philic (Ti, Sm, U..) character react in a similar way with the carbonyl compounds. If the uranium compounds are less used than those of the titanium in the field of the organic synthesis applications, they are precious auxiliaries and excellent models for reactions mechanisms study and for the synthesis methods optimization. (O.M.). 284 refs.}
place = {France}
year = {1997}
month = {Jul}
}