The Intermetalloid Clusters [Ni2Bi12]4+ and [Rh2Bi12]4+ - Ionothermal Synthesis, Crystal Structures, and Chemical Bonding

被引：8

作者：

Groh, Matthias F. ^{[1
,2
]}

Mueller, Ulrike ^{[1
]}

Isaeva, Anna ^{[1
]}

Ruck, Michael ^{[1
,3
]}

机构：

[1] Tech Univ Dresden, Dept Chem & Food Chem, D-01062 Dresden, Germany

[2] Univ Cambridge, Dept Chem, Lensfield Rd, Cambridge CB2 1EW, England

[3] Max Planck Inst Chem Phys Solids, Nothnitzer Str 40, D-01187 Dresden, Germany

来源：

ZEITSCHRIFT FUR ANORGANISCHE UND ALLGEMEINE CHEMIE | 2019年 / 645卷 / 03期

关键词：

Transition metals; Ionic liquids; Bismuth; Coordination compounds; Cluster compounds; MOLECULAR-ORBITAL THEORY; EXTENDED BASIS-SETS; IONIC LIQUIDS; ORGANOMETALLIC COMPOUNDS; ELECTRON LOCALIZATION; BI-6(2+) POLYCATIONS; ENERGY; METAL; DELOCALIZATION; APPROXIMATION;

D O I：

10.1002/zaac.201800441

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The intermetalloid clusters [M2Bi12](4+) (M = Ni, Rh) were synthesized as halogenido-aluminates in Lewis-acidic ionic liquids. The reaction of bismuth and NiCl2 in [BMIm]Cl5AlCl(3) (BMIm = 1-butyl-3-methylimidazolium) at 180 degrees C yielded black, triclinic crystals of [Ni2Bi12][AlCl4](3)[Al2Cl7]. Black, monoclinic (P2(1)/m) crystals of [Rh2Bi12][AlBr4](4) precipitated after dissolving the cluster salt Bi12-xRhX13-x (X = Cl, Br; 0 < x < 1) in [BMIm]Br4.1AlBr(3) at 140 degrees C. In the cationic cluster [Ni2Bi12](4+), the nickel atoms center two base-sharing square antiprisms of bismuth atoms (symmetry close to D-4h). The valence-electron-poorer rhodium-containing cluster is a distorted variant of this motif: the terminating Bi-4 rings are folded to bicyclic butterflies and the central square splits into two dumbbells (symmetry close to D-2h). DFT-based calculations and real-space bonding analyses place the intermetalloid units between a triple-decker complex and a conjoined Wade-Mingos cluster.

引用

页码：161 / 169

页数：9

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