[Ni(CO)4]+ as NiI Synthon: Synthesis and Characterization of NiI Half‐Sandwich and Sandwich Cations

Abstract

AbstractThe stable, easily accessible salt [Ni(CO)4]+[F{Al(ORF)3}2]− (RF=C(CF3)3) was used as a NiI synthon to generate the novel half‐sandwich complexes [Ni(arene)(CO)2]+ (arene=C6H6, o‐dfb=1,2‐F2C6H4). By irreversible removal of CO from the equilibrium, even the rather endergonic reaction to a [Ni(o‐dfb)2]+ salt was successful (ΔrG°(solv)=+78 kJ mol−1). The latter displays an unprecedented slipped η3,η3‐sandwich structure and is the ultimate synthon to NiI‐chemistry.