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Reactions of sulfurdiimines and sulfinylanilines with [AlMe3]2

By G. van Koten, J.M. Klerks, R. van Vliet and K. Vrieze

Abstract

Reaction of sulfurdiimines RN@?S@?NR and the isoelectronic and structurally analogous sulfinylanilines RN@?S@?O with [Me{3}Al]{2} gave the complexes [Me{2}Al{RNS(Me)NR} ]{2}(R @? 4-MeC{6}H{4}, 4- ClC{6}H{4}, 2, 6-Me{2}C{6}H{3}) and [Me{2}Al{RNS(Me)O}]{2}(R = Me, C{6}H{5}, 4-MeC{6}H{4}, 4-ClC{6}H{4}, 2,6-Me{2}C{6}H{3} and 2,4,6-Me{3}C{6}H{2}) in which the S atom is methylated. Reaction of [Me{2}Al{RNS-(Me)NR}]{2} with HgCl{2} or SnCl{2} results in replacement of the methyl groups on the Al atom by Cl to give the dimeric [Cl{2}Al{RNS(Me)NR}]{2} for R @? 2,6-Me{2}C{6}H{3}.The dimeric complexes [Me{2}Al{RNS(Me)X}] (X @? O, NR) exist in two conformations which undergo intramolecular interconversion in the case of the sulfurdiimine compounds, and probably also for the sulfinylaniline derivatives. In the latter case intermolecular exchange via a monomeric species also plays a role. This monomer may be observed in dilute solutions. While the sulfinylaniline compounds are stable in solution (CDCl{3}, pyridine), the sulfurdiimine compounds decompose slowly in CDCl{3} and rapidly in pyridine to produce diazoaryls, some RNH{2}, and polymeric products. The alcoholysis of the sulfudiimine-Al complexes also usually give similar products. The possible roles of nitrene N@?R and radical RNS@?ME intermediates in the decompositions are discussed

Topics: Scheikunde
Year: 1981
OAI identifier: oai:dspace.library.uu.nl:1874/6427
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