An Unprecedented Cluster Unit in (BMIm)2[Hf9Cl14H8(AlCl4)6

Abstract

AbstractThe reduction of HfCl4 with Li[AlH4] under ionothermal conditions using (BMIm)[AlCl4] as solvent and as reactant gives the compound (BMIm)2[Hf9Cl14H8(AlCl4)6] in moderate yield. It contains nona‐nuclear metalloid cluster units with an unprecedented arrangement of the metal atoms. This can be described by a polyhedron consisting of two trigonal bipyramids, which are fused in one basal Hf atom. The edges of the Hf9 polyhedron are bridged by Cl atoms and the apical sites Cl‐bonded to [AlCl4]− anions. These bridge the cluster units into 1D cluster strands. The metal atom polyhedron can be constructed by a step‐wise distortion of a body centred cube. DFT calculations on [Hf9Cl14H(8‐x)(AlCl4)6]2− units for different numbers of hydrogen atoms (x=8–0) at the UPBE‐D3/def2‐TZVP level of theory indicate significant metal‐metal bonding. These calculations supported strongly the presence of hydridic H atoms bridging triangular faces of the metal atom skeleton. The most stable cluster anion is calculated for eight H atoms present in the cluster unit.