Cationic Boron‐Centred Hexanuclear Zirconium Cluster Compounds with Nitrilo Ligands and [M III Cl 4 ] – Counter Ions: [(Zr 6 B)Cl 12 (CH 3 CN) 6 ][M III Cl 4 ] with M III = Al, Ga, In

Molecular zirconium cluster ions were excised from the solid‐state precursor K 2 [(Zr 6 B)Cl 15 ] using acetonitrile as the solvent. With the addition of the Lewis acids AlCl 3 , GaCl 3 or InCl 3 the chemical equilibria between the different cluster species in solution of the type [(Zr 6 B)Cl i 12 (CH 3 CN) 6– x Cl a x ] 1– x with 0 ≤  x  ≤ 6 are shifted such that only one species is present, with x = 0, i.e. [(Zr 6 B)Cl i 12 (CH 3 CN) 6 ] + . This was confirmed by 11 B NMR spectroscopy. From the corresponding solutions four crystalline compounds were obtained, [(Zr 6 B)Cl 12 (CH 3 CN) 6 ][AlCl 4 ] ( 1 ), [(Zr 6 B)Cl 12 (CH 3 CN) 6 ][AlCl 4 ] · CH 3 CN ( 2 ), [(Zr 6 B)Cl 12 (CH 3 CN) 6 ][GaCl 4 ] · CH 3 CN ( 3 ) or [(Zr 6 B)Cl 12 (CH 3 CN) 6 ][InCl 4 ] ( 4 ). The single‐crystal X‐ray structures of 1 – 3 were determined. They all crystallize in the space group P $\bar {1}$ 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 [(Zr 6 B)Cl 12 (CH 3 CN) 6 ] + cluster cations, [M III Cl 4 ] – anions (M III = Al, Ga or In) and in the case of 2 and 3 cocrystallized CH 3 CN molecules.