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"Mono- and Bimetallic (NacNac)Ni Cyclopentadienyl Complexes"


  • DocumentId
  • bai2006
  • Ausgabe
  • 2006, 25 (25) 
  • Seiten
  • 5870-5878 
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  • Abstract
  • Complexes of the form (Nacnac)Ni(è5-L) (L ) Cp (3), indenyl (4)) are readily prepared and have been protonated to generate the corresponding cationic species [(HNacNac)Ni(è5-L)][B(C6F5)4] (L ) Cp (5), indenyl (6)). While the symmetric compound 3 is paramagnetic, disruption of the symmetry in 4-6results in diamagnetism. The species [((Nacnac)Ni)2(í-è5:è5-Cp)][B(C6F5)4] (7) was prepared in an unusual fashion from the reaction of [(NacNac)Ni]2(è6:è6-C6H5Me) (2) with [Ph3C][B(C6F5)4] and Cp2ZrMe2, while compound 3 serves as a synthon to the neutral bimetallic Ni(II)/Ni(I) species [((Nacnac)Ni)2(í-è2:è2-Cp)] (8). Compounds 7 and 8 are readily interconverted electrochemically. Consideration of the molecular orbitals reveals that the unpaired electron in 8 prompts alteration of the nature of the bridging cyclopentadienyl ligand between the metal centers. Crystal structures of 3-5, 7, and 8 are reported. 
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