Transformations of the cyclo-P4 ligand in [Cp′′′Co(η4-P4)]

Abstract

The reactivity of the cyclo-P₄ ligand complex [Cp′′′Co(η⁴-P₄)] (1) (Cp′′′ = 1,2,4-tri-tert-butyl-cyclopentadienyl) towards reduction and main group nucleophiles was investigated. By using K[CpFe(CO)₂], a selective reduction to the dianionic complex [(Cp′′′Co)₂(μ,η³:η³-P₈)]²⁻ (2) was achieved. The reaction of 1 with ^tBuLi and LiCH₂SiMe₃ as carbon-based nucleophiles yielded [Cp′′′Co(η³-P₄R)]⁻ (R = ^tBu (4), CH₂SiMe₃ (7)), which, depending on the reaction conditions, undergo subsequent reactions with another equivalent of 1 to form [(Cp′′′Co)₂(μ,η³:η³-P₈R)]⁻ (R = ^tBu (5), CH₂SiMe₃ (8)). In the case of 4, a different pathway was observed, namely a dimerisation followed by a fragmentation into [Cp′′′Co(η³-P₅^tBu₂)]⁻ (6) and [Cp′′′Co(η³-P₃)]⁻ (3). With OH⁻ as an oxygen-based nucleophile, the synthesis of [Cp′′′Co(η³-P₄(O)H)]⁻ (9) was achieved. All compounds were characterized by X-ray crystal structure analysis, NMR spectroscopy and mass spectrometry. Their electronic structures and reaction behavior were elucidated by DFT calculations.