Abstract
Cyclic α-alkoxyvinylnickel(II) complexes of the types trans-[NiRL2([graphic omitted])] and trans-[NiRL2-([graphic omitted])](R = C6H2Me3-2,4,6 or C6Cl5 and L = PMe3 or PMe2Ph) have been prepared from trans-[NiRL2X](X = Cl or Br) and 2,3-dihydro-5-lithiofuran or 2,3-dihydro-6-lithiopyran. Treatment of these complexes with aqueous perchloric acid gives the corresponding cationic cyclic carbene complexes, trans-[NiRL2([graphic omitted])][ClO4] and trans-[NiRL2([graphic omitted])][ClO4]. The carbene complexes of trans-Ni(C6H2Me3-2,4,6)L2 have a lower Bronsted acidity than those of trans-Ni(C6Cl5)L2 and the barriers to rotation of the cyclic alkoxyvinyl groups and the cyclic alkyl(alkoxy)carbene ligands about the Ni–C bond are lower for the former complexes than for the latter. These results are intepreted in terms of the stronger trans influence of the C6H2Me3-2,4,6 group.
Published Version
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