Synthesis and Properties of [NiCp*(2,5‐tBu2PC4H2)], a 20‐Valence‐Electron Phosphanickelocene

Abstract

The reaction of the bulky phospholide salt Li(2,5-tBu2PC4H2) x 2THF (1; THF = tetrahydrofuran) with [NiCp*(acac)] (HCp* = pentamethylcyclopentadiene, Hacac = acetylacetone) gives the green air-sensitive phosphanickelocene [NiCp*(2,5-tBu2PC4H2)] (2) in yields of about 85%. An X-ray structural determination of 2 shows long Ni-ring bonds and "delocalised" ring P-C and C-C bonds characteristic of a classical 20-valence-electron (ve) nickelocene. The electronic structure of 2 has been clarified through a combined Amsterdam density functional (ADF) and photoelectron spectroscopic study, which indicates that the higher lying semi-occupied molecular orbital (SOMO) (-5.82 eV) has a' symmetry and that the phosphorus "lone pair" is energetically low-lying (-8.15 eV). Oxidation of phosphanickelocene 2 by AgBF4 occurs quantitatively to give the corresponding air-sensitive orange phosphanickelocenium salt [NiCp*(2,5-tBu2PC4H2)][BF4] (3). This complex has also been characterised by an X-ray crystallographic study, which reveals long Ni-C(alpha) and short C(alpha)-C(beta) bonds in the phospholyl ligand indicative of a SOMO having a'' symmetry. PMe3 reacts with 2 at room temperature to provoke a ring-slip reaction that gives the 18ve complex [NiCp*eta1-(2,5-tBu2PC4H2)(PMe3)] (4), but shows no reaction with the phosphanickelocenium salt 3 under the same conditions.