Influence of basicity and steric effects on the metathesis of olefinic amines

C. Edwige*, A. Lattes, J. P. Laval, R. Mutin, Jean-Marie Maurice Basset, R. Nouguier

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

24 Scopus citations

Abstract

Metathesis of olefinic amines has been studied with two purposes: (i) to try to carry out at a stoichiometric (or slightly catalytic) level metathesis of olefinic amines to obtain telechelic compounds; (ii) to try to find which parameters play a role in the catalytic process. Two types of catalytic systems were found to be moderately active in the metathesis of olefinic amines: W(CO)5L {A figure is presented} or W(CO)3(Arene) (Arene = benzene, toluene, mesitylene) associated with a large excess of C2H5AlCl2 and O2. M(NO)2X2L2 associated with an excess of C2H5AlCl2 (X = Cl, Br; M = Mo, W). The substituents on the nitrogen were found to determine the resulting reactivity of the olefinic amine: steric as well as electronic effects play a role on the acid-base equilibrium between the amine and the Lewis acid cocatalyst. The distance between the double bond and the amine group shows a sharp maximum for olefins of the type CH2CH(CH2)3N(R)(R′). The results are tentatively explained on the basis of an intramolecular stabilization of the metallocarbene moiety by the amine group; this would increase the lifetime of the catalyst. Stereochemical studies seem to indicate that there is no modification of stereochemistry between functionalized and non-functionalized olefins. Consequently the intramolecular stabilization of the metallocarbene moiety and the amine group does not occur in the metallo-cyclobutane transition state formation.

Original languageEnglish (US)
Pages (from-to)297-311
Number of pages15
JournalJournal of molecular catalysis
Volume8
Issue number1-3
DOIs
StatePublished - Jan 1 1980

ASJC Scopus subject areas

  • Engineering(all)

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