Dataset Information

Crystal structure of the formal 20 electron zirconocene penta-fulvene complex Cp₂Zr(?⁵,?¹-adamantyl-idene-penta-fulvene):toluene:n-hexane = 1:0.125:0.125.

ABSTRACT: The crystal structure of a solvated zirconocene penta-fulvene complex with a bulky adamantyl-idene substitution pattern, namely (?⁵,?¹-adamantyl-idene-penta-fulvene)bis-(?⁵-cyclo-penta-dien-yl)zirconium(IV)-toluene-n-hexane (8/1/1), [Zr(C₁₅H₁₈)(C₅H₅)₂]·0.125C₇H₈·0.125C₆H₁₄, is reported. Reducing zirconocene dichloride with magnesium results in the formation of a low-valent zirconocene reagent that reacts readily with adamantyl-idene-penta-fulvene to give the aforementioned complex. Single crystal X-ray diffraction proves the dianion-like ?⁵:?¹ binding mode of the fulvene ligand to the central Zr^IV atom. The asymmetric unit contains four independent mol-ecules of [?⁵:?¹-adamantyl-idene-penta-fulvene]bis-[(?⁵)-cyclo-penta-dien-yl]zirconium(IV), together with half a mol-ecule of toluene disordered with half a mol-ecule of n-hexane (the solvent mol-ecules have no direct influence on the complex). In each of the four complex mol-ecules, the central Zr^IV atom has a distorted tetra-hedral coordination environment. The measured crystal consisted of two domains with a refined ratio of 0.77:0.23.

SUBMITTER: Fischer M

PROVIDER: S-EPMC5730232 | biostudies-literature | 2017 Dec

REPOSITORIES: biostudies-literature

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Crystal structure of the formal 20 electron zirconocene penta-fulvene complex Cp2Zr(η5,η1-adamantyl-idene-penta-fulvene):toluene:n-hexane = 1:0.125:0.125.

Fischer Malte M Schmidtmann Marc M Beckhaus Rüdiger R

Acta crystallographica. Section E, Crystallographic communications 20171103 Pt 12

The crystal structure of a solvated zirconocene penta-fulvene complex with a bulky adamantyl-idene substitution pattern, namely (η5,η1-adamantyl-idene-penta-fulvene)bis-(η5-cyclo-penta-dien-yl)zirconium(IV)-toluene-n-hexane (8/1/1), [Zr(C15H18)(C5H5)2]·0.125C7H8·0.125C6H14, is reported. Reducing zirconocene dichloride with magnesium results in the formation o ...[more]

PMID: 29250395

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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.

Dataset Information

Crystal structure of the formal 20 electron zirconocene penta-fulvene complex Cp₂Zr(?⁵,?¹-adamantyl-idene-penta-fulvene):toluene:n-hexane = 1:0.125:0.125.

Publications

Crystal structure of the formal 20 electron zirconocene penta-fulvene complex Cp<sub>2</sub>Zr(η<sup>5</sup>,η<sup>1</sup>-adamantyl-idene-penta-fulvene):toluene:<i>n</i>-hexane = 1:0.125:0.125.

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Dataset Information

Crystal structure of the formal 20 electron zirconocene penta-fulvene complex Cp2Zr(?5,?1-adamantyl-idene-penta-fulvene):toluene:n-hexane = 1:0.125:0.125.

Publications

Crystal structure of the formal 20 electron zirconocene penta-fulvene complex Cp<sub>2</sub>Zr(η<sup>5</sup>,η<sup>1</sup>-adamantyl-idene-penta-fulvene):toluene:<i>n</i>-hexane = 1:0.125:0.125.

Similar Datasets

OmicsDI is part of the ELIXIR infrastructure

Tweets

Crystal structure of the formal 20 electron zirconocene penta-fulvene complex Cp₂Zr(?⁵,?¹-adamantyl-idene-penta-fulvene):toluene:n-hexane = 1:0.125:0.125.