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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 ^t BuLi and LiCH₂SiMe₃ as carbon-based nucleophiles yielded [Cp'''Co(η³-P₄R)]^- (R = ^t Bu (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 = ^t Bu (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 ^t Bu₂)]^- (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.

SUBMITTER: Piesch M

PROVIDER: S-EPMC8159306 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Project description:Neutral {CpFeII(CO)2[SnII(Pc•3-)]} {Cp is cyclopentadienyl (1, 2) or Cp* is pentamethylcyclopentadienyl (3); Pc: phthalocyanine}, {Cp*FeII(CO)2[SnII(Nc•3-)]} (4, Nc: naphthalocyanine), and {CpFeII(CO)2[SnII(TPP•3-)]} (5, TPP: tetraphenylporphyrin) complexes in which CpFeII(CO)2 fragments (Cp: Cp or Cp*) are coordinated to SnII(macrocycle•3-) have been obtained. The product complexes were obtained at the reaction of charge transfer from CpFeI(CO)2 (Cp: Cp or Cp*) to [SnII(macrocycle2-)] to form the diamagnetic FeII and paramagnetic radical trianionic macrocycles. As a result, these formally neutral complexes contain S = 1/2 spins delocalized over the macrocycles. This provides alternation of the C-Nimine or C-Cmeso bonds in the macrocycles, the appearance of new bands in the near-infrared spectra of the complexes, and blue shift of both Soret and Q-bands. The {CpFeII(CO)2SnII(macrocycle•3-)} units (Cp: Cp or Cp*, macrocycle: Pc or Nc) form closely packed π-stacking dimers in 1 and 3 or one-dimensional chains in 2 and 4 with effective π-π interaction between the macrocycles. Such packing allows strong antiferromagnetic coupling between S = 1/2 spins. Magnetic interaction can be described well by the Heisenberg model for the isolated dimers in 1 and 3 with exchange interaction J/k B = -78 and -85 K, respectively. Magnetic behavior of 2 and 4 is described well by the model that includes contributions from an antiferromagnetically coupled S = 1/2 dimer (J intra) and a Heisenberg S = 1/2 chain with alternating antiferromagnetic spin exchange between the neighbors (J inter). Compound 2 demonstrates large intradimer interaction of J intra/k B = -54 K and essentially weaker interdimer exchange interactions of J inter/k B = -6 K, whereas compound 4 shows strong magnetic coupling of spins within the dimers (J intra/k B = -170 K) as well as between the dimers (J inter/k B = -40 K). Compound {CpFeII(CO)2[SnII(TPP•3-)]} (5) shows no π-π interactions between the porphyrin macrocycles, and magnetic coupling is weak in this case (Weiss temperature is -5 K). Preparation of a similar complex with indium(III) chloride phthalocyanine yields {CpFe(CO)2[In(Pc2-)]} (6). In this complex, indium(III) atoms are reduced instead of the phthalocyanine macrocycles that explains electron paramagnetic resonance silence of 6 in the 4-295 K range.

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

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

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