Conversion of imine ligands in allyl–nickel(II) complexes
摘要:
Interaction of Ni(allyl)(2) and bidentate nitrogen-containing ligands (phenanthroline-1,10; bis(2,6-diisopropylphenyl)diazabutadiene) has been studied. It has been shown that coordination of diimine ligands proceeds with transfer of an allylnickel group to the diimine frame and formation of a covalent Ni-N bond giving rise to imine(amide)Ni(II) complexes. In the case of phenanthroline dearomatization of one heteroaromatic ring takes place. The low-spin imine(amide)allyl complexes(allyl)Ni(C(15)H(15)N(2)) (1) and (allyl)Ni(C(29)H(42)N(2)) (3) have been isolated as crystals and characterized by solution spectroscopy. Combining two molar equivalents of phenanthroline-1,10 with Ni(allyl)(2) results in the transfer of both allyl groups and formation of the high-spin imine(amide)Ni(II) complex Ni(C(15)H(15)N(2))(2) (2). (C) 2009 Elsevier B.V. All rights reserved.
2D-NMR and EPR study of the activation of π-allyl group within the coordination sphere of the imine–amide complex of nickel(II) by the coordination of PMe
作者:Peter B. Kraikivskii、Vitaly V. Saraev、Reinhard Meusinger、Victoria V. Bocharova、Igor A. Ushakov、Stanislav K. Petrovskii
DOI:10.1016/j.jorganchem.2012.05.035
日期:2012.9
π-allyl imine–amide complex of nickel(II) affects the nickeloxidation state and leads to the irreversible elimination of the allyl group in the form of a cyclodimerization product. The coordination of PMe3 to allyl imine–amide complex 1 brings about the formation of phosphine allyl imine–amide complex of nickel(II) 3. In solution it spontaneously disproportionates giving nickel(I) complex 4 and cyclohexene