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Metallocages for Metal Anions: Highly Charged [Co@Ge₉ ]^5- and [Ru@Sn₉ ]^6- Clusters Featuring Spherically Encapsulated Co^1- and Ru^2- Anions.

ABSTRACT: Endohedral clusters count as molecular models for intermetallic compounds-a class of compounds in which bonding principles are scarcely understood. Herein we report soluble cluster anions with the highest charges on a single cluster to date. The clusters reflect the close analogy between intermetalloid clusters and corresponding coordination polyhedra in intermetallic compounds. We now establish Raman spectroscopy as a reliable probe to assign for the first time the presence of discrete, endohedrally filled clusters in intermetallic phases. The ternary precursor alloys with nominal compositions "K₅ Co_1.2 Ge₉ " and "K₄ Ru₃ Sn₇ " exhibit characteristic bonding modes originating from metal atoms in the center of polyhedral clusters, thus revealing that filled clusters are present in these alloys. We report also on the structural characterization of [Co@Ge₉ ]^5- (1a) and [Ru@Sn₉ ]^6- (2a) obtained from solutions of the respective alloys.

SUBMITTER: Witzel BJL

PROVIDER: S-EPMC6771791 | biostudies-literature | 2019 Sep

REPOSITORIES: biostudies-literature

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Publications

Metallocages for Metal Anions: Highly Charged [Co@Ge9 ]5- and [Ru@Sn9 ]6- Clusters Featuring Spherically Encapsulated Co1- and Ru2- Anions.

Witzel Benedikt J L BJL Klein Wilhelm W Dums Jasmin V JV Boyko Marina M Fässler Thomas F TF

Angewandte Chemie (International ed. in English) 20190821 37

Endohedral clusters count as molecular models for intermetallic compounds-a class of compounds in which bonding principles are scarcely understood. Herein we report soluble cluster anions with the highest charges on a single cluster to date. The clusters reflect the close analogy between intermetalloid clusters and corresponding coordination polyhedra in intermetallic compounds. We now establish Raman spectroscopy as a reliable probe to assign for the first time the presence of discrete, endohed ...[more]

PMID: 31298780

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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

Metallocages for Metal Anions: Highly Charged [Co@Ge₉ ]^5- and [Ru@Sn₉ ]^6- Clusters Featuring Spherically Encapsulated Co^1- and Ru^2- Anions.

Publications

Metallocages for Metal Anions: Highly Charged [Co@Ge<sub>9</sub> ]<sup>5-</sup> and [Ru@Sn<sub>9</sub> ]<sup>6-</sup> Clusters Featuring Spherically Encapsulated Co<sup>1-</sup> and Ru<sup>2-</sup> Anions.

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