Dataset Information

A Neutral "Aluminocene" Sandwich Complex: ?1 - versus ?5 -Coordination Modes of a Pentaarylborole with ECp* (E=Al, Ga; Cp*=C5 Me5 ).

ABSTRACT: The pentaaryl borole (Ph*C)4 BXylF [Ph*=3,5-tBu2 (C6 H3 ); XylF =3,5-(CF3 )2 (C6 H3 )] reacts with low-valent Group?13 precursors AlCp* and GaCp* by two divergent routes. In the case of [AlCp*]4 , the borole reacts as an oxidising agent and accepts two electrons. Structural, spectroscopic, and computational analysis of the resulting unprecedented neutral ?5 -Cp*,?5 -[(Ph*C)4 BXylF ] complex of AlIII revealed a strong, ionic bonding interaction. The formation of the heteroleptic borole-cyclopentadienyl "aluminocene" leads to significant changes in the 13 C?NMR chemical shifts within the borole unit. In the case of the less-reductive GaCp*, borole (Ph*C)4 BXylF reacts as a Lewis acid to form a dynamic adduct with a dative 2-center-2-electron Ga-B bond. The Lewis adduct was also studied structurally, spectroscopically, and computationally.

SUBMITTER: Sindlinger CP

PROVIDER: S-EPMC6856865 | biostudies-literature | 2019 Oct

REPOSITORIES: biostudies-literature

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Publications

A Neutral "Aluminocene" Sandwich Complex: η1 - versus η5 -Coordination Modes of a Pentaarylborole with ECp* (E=Al, Ga; Cp*=C5 Me5 ).

Sindlinger Christian P CP Ruth Paul Niklas PN

Angewandte Chemie (International ed. in English) 20190910 42

The pentaaryl borole (Ph*C)4 BXylF [Ph*=3,5-tBu2 (C6 H3 ); XylF =3,5-(CF3 )2 (C6 H3 )] reacts with low-valent Group 13 precursors AlCp* and GaCp* by two divergent routes. In the case of [AlCp*]4 , the borole reacts as an oxidising agent and accepts two electrons. Structural, spectroscopic, and computational analysis of the resulting unprecedented neutral η5 -Cp*,η<s ...[more]

PMID: 31390132

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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

A Neutral "Aluminocene" Sandwich Complex: ?1 - versus ?5 -Coordination Modes of a Pentaarylborole with ECp* (E=Al, Ga; Cp*=C5 Me5 ).

Publications

A Neutral "Aluminocene" Sandwich Complex: η<sup>1</sup> - versus η<sup>5</sup> -Coordination Modes of a Pentaarylborole with ECp* (E=Al, Ga; Cp*=C<sub>5</sub> Me<sub>5</sub> ).

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