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Cationic Boron-Centred Hexanuclear Zirconium Cluster Compounds with Nitrilo Ligands and [MIIICl4] Counter Ions: [(Zr6B)Cl12(CH3CN)6][MIIICl4] with MIII = Al, Ga, In

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  • Dedicated to Professor John D. Corbett on the occasion of his 85th birthday

Abstract

Molecular zirconium cluster ions were excised from the solid-state precursor K2[(Zr6B)Cl15] using acetonitrile as the solvent. With the addition of the Lewis acids AlCl3, GaCl3 or InCl3 the chemical equilibria between the different cluster species in solution of the type [(Zr6B)Cli12(CH3CN)6–xClax]1–x with 0 ≤ x ≤ 6 are shifted such that only one species is present, with x = 0, i.e. [(Zr6B)Cli12(CH3CN)6]+. This was confirmed by 11B NMR spectroscopy. From the corresponding solutions four crystalline compounds were obtained, [(Zr6B)Cl12(CH3CN)6][AlCl4] (1), [(Zr6B)Cl12(CH3CN)6][AlCl4]·CH3CN (2), [(Zr6B)Cl12(CH3CN)6][GaCl4]·CH3CN (3) or [(Zr6B)Cl12(CH3CN)6][InCl4] (4). The single-crystal X-ray structures of 13 were determined. They all crystallize in the space group Pequation image with two formula units per unit cell with the following cell parameters: 1: a = 12.1012(4), b = 12.7463(4), c = 17.2155(5) Å, α = 111.847(2), β = 90.243(2), γ = 117.263(2)°; 2: a = 12.037(5), b = 12.787(5), c = 17.675(7) Å, α = 92.63(1), β = 109.57(1), γ = 116.01(1)°; 3: a = 12.0926(4), b = 12.7565(4), c = 17.6895(6) Å, α = 92.757(2), β = 109.806(2), γ = 116.116(1)°. All these compounds contain molecular [(Zr6B)Cl12(CH3CN)6]+ cluster cations, [MIIICl4] anions (MIII = Al, Ga or In) and in the case of 2 and 3 cocrystallized CH3CN molecules.

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