Abstract
The potassium salt [K([18]crown-6)(THF)(2)]-[Cp*Fe(eta(4)-2,4,6-triphenylphosphinine)}] (K1, Cp* = C5Me5) can be isolated in 68% yield by reacting the anionic naphthalene complex [K([18]crown-6){Cp*Fe(eta(4)-C10H8)}] (C10H8 = naphthalene) with 2,4,6-triphenylphosphinine. Compound K1 reacts with water to afford [K([18]-crown-6)]{Cp*Fe(eta(4)-2,4,6-triphenyl-2,3-dihydrophosphinine 1-oxide)}] (K2) ...
Abstract
The potassium salt [K([18]crown-6)(THF)(2)]-[Cp*Fe(eta(4)-2,4,6-triphenylphosphinine)}] (K1, Cp* = C5Me5) can be isolated in 68% yield by reacting the anionic naphthalene complex [K([18]crown-6){Cp*Fe(eta(4)-C10H8)}] (C10H8 = naphthalene) with 2,4,6-triphenylphosphinine. Compound K1 reacts with water to afford [K([18]-crown-6)]{Cp*Fe(eta(4)-2,4,6-triphenyl-2,3-dihydrophosphinine 1-oxide)}] (K2) with a novel 2,3-dihydrophosphinine 1-oxide ligand. Oxidation of K1 with one equivalent of ferrocenium hexafluorophosphate yields the PP-bonded diphosphinine complex [Cp*Fe(eta(5)-2,4,6-triphenylphosphinine)](22)(3), while the iodide salt [Cp*Fe(eta(6)-2,4,6-triphenylphosphinine)]I (4) can be obtained by reacting K1 with one equivalent of iodine. Reactions of 4 with LiNMe2, Cp*Li, LiBHEt3, and Ga(nacnac(Dipp)) (nacnac(Dipp) = HC{C(Me)N(C6H3-2,6-iPr(2))}(2)) afford [Cp*Fe(eta(5)-1-dimethylamino-2,4,6-triphenylphosphacyclohexadienyl)] (5), [Cp*Fe(eta(5)-1-(eta(1)-Cp*)-2,4,6-triphenylphosphacyclohexadienyl)] (6), [Cp*Fe(eta(5)-1-hydro-2,4,6-triphenylphosphacyclohexadienyl)] (7), and [Cp*Fe((eta(5)-1-{Ga(nacnac(Dipp))I}-2,4,6-triphenylphosphacyclohexadienyl] (8). The molecular structures of 58 display eta(5)-coordinated lambda(3)sigma(3)-phosphinine anions. All new complexes were fully characterized by spectroscopic techniques (H-1, C-13, and P-31 NMR, UVvis, and IR spectroscopy), elemental analysis, and X-ray crystallography. The electronic structures of these new phosphinine complexes were investigated theoretically at the DFT level, using molecular orbital and population analyses. The nature of the electronic transitions observed in the UVvis spectra was analyzed using TD-DFT calculations.
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