Reatividade de diazirinas e diaziridinas com compostos de paladio (II) em solventes proticos e aproticos
AUTOR(ES)
Heloise de Oliveira Pastore
DATA DE PUBLICAÇÃO
1988
RESUMO
In this work, 3,3-pentamethylenediaziridine, N-methyl-3,3-pentamethylenediaziridine and N-cyclohexyl-3,3-pentamethylene diaziridine were prepared, as described in the literature. The coordination of these diaziridines with palladium(II) compounds was studied; these heterocycles react with bis-benzoni-trile-dichloropalladium(II), yielding air stable complexes, which retain the ring system. These complexes rearrange, thermally, in methanol, forming compounds which show a substituted hydrazine ligand, still bonded to the metal atom. The diaziridines are n ligands and bind to the palladium atom through only one nitrogen atom. The sodium azide and boron trifluoride reactions with the coordinated heterocycles, form products which show a cleavage of one bond, the result of nucleophilic or eletrophilic attack. In the new complexes formed, the organic fragment remains attached to the metal atom. On the other band, free 3,3-pentamethylenediaziridine acts as a nucleophile on coordinate ethylene. In this way, the reaction of di-m-chloro-dichlorobis (ethylene) dipalladium(II) and this diaziridine yield a new organometallic complex, cyclometalted, with five members, which retains the ring system. The 3,3-pentamethylenediazirine, obtained by the 3, 3-pentamethylenediaziridine oxidation, reacts stoichiometrically, with bis-benzonitrile-dichloropalladium (II), in benzene, producing molecular nitrogen, cyclohexene and palladium dichloride. This diazirine also reacts with di-m-chloro-dichlorobis (cyclohexene) dipalladium (II), catalytically, in benzene, at room temperature, and also produces molecular nitrogen and cyclohexene, in good yields.
ASSUNTO(S)
paladio compostos de diazo - reatividade (quimica) solventes organicos
ACESSO AO ARTIGO
http://libdigi.unicamp.br/document/?code=vtls000048092Documentos Relacionados
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