Inhaltszusammenfassung

The reaction of terephthal-bis-imines with Fe-2(CO)(9) proceeds via a C-H activation reaction in the ortho position with respect to one of the imine functions. The corresponding hydrogen atom is shifted towards the former imine carbon atom producing a methylene group instead. The dinuclear iron complexes formed by this reaction sequence and showing no coordination of the second imine group were isolated from reactions of bis-imines with both phenyl and cyclohexyl substituents at the imine nit...The reaction of terephthal-bis-imines with Fe-2(CO)(9) proceeds via a C-H activation reaction in the ortho position with respect to one of the imine functions. The corresponding hydrogen atom is shifted towards the former imine carbon atom producing a methylene group instead. The dinuclear iron complexes formed by this reaction sequence and showing no coordination of the second imine group were isolated from reactions of bis-imines with both phenyl and cyclohexyl substituents at the imine nitrogen atoms. In addition, we observed three different reaction pathways of the second imine substituent of the starting material which is obviously thus influenced by the fact that the first one is coordinating an Fe-2(CO)(6) moiety. If the organic substituent at the imine nitrogen atoms is a phenyl group the formation of a trinuclear complex is achieved in which an additional Fe(CO)(3) group is coordinating the CN double bond and one of the carbon-carbon bonds of the central phenyl ring in an eta (4)-fashion. The same reaction leads to the isolation of a tetranuclear iron-carbonyl compound in which both imine substituents were transformed via the pathway described above, each building up dinuclear subunits. In contrast to this the reaction of a bis-imine with cyclohexyl groups at the imine nitrogen and thus an enhanced nucleophilicity leads to the formation of a tetranuclear complex in which only one imine group reacts under C-H activation with subsequent hydrogen migration towards the former imine carbon atom. The second imine substituent also shows a C-H activation reaction in the ortho position with respect to the imine group but the corresponding hydrogen atom is transferred to one of the aromatic carbon atom of the central phenyl ring of the ligand. The C=N double bond remains unreacted and only coordinates the second Fe,(CO), moiety via the nitrogen lone pair. (C) 2000 Elsevier Science S.A. All rights reserved. » weiterlesen» einklappen

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