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

被引：0

作者：

Jablonski, Jonas ^{[1
]}

Bresien, Jonas ^{[2
]}

Koeckerling, Martin ^{[1
,3
]}

机构：

[1] Univ Rostock, Inst Chem, Anorgan Festkorperchem, Albert Einstein Str 3a, D-18059 Rostock, Germany

[2] Univ Rostock, Inst Chem, Anorgan & Elementorgan Chem, Albert Einstein Str 3a, D-18059 Rostock, Germany

[3] Univ Rostock, Dept Life Light & Matter, D-18051 Rostock, Germany

来源：

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY | 2021年 / 2021卷 / 46期

关键词：

Cluster compounds; Density functional calculations; Electronic structure; Hafnium; Metalloid clusters; Structure elucidation; IONIC LIQUIDS; NONANUCLEAR; COMPLEXES; CHEMISTRY; CRYSTALLIZATION; NIOBIUM; VALENCE; FAMILY;

D O I：

10.1002/ejic.202100191

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The 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 Hf-9 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.

引用

页码：4776 / 4780

页数：5

共 37 条

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