Hexatellurium Rings in Coordination Polymers and Molecular Clusters: Synthesis and Crystal Structures of [M(Te6)]X3 (M = Rh, Ir; X = Cl, Br, I) and [Ru2(Te6)](TeBr3)4(TeBr2)2

Hexatellurium Rings in Coordination Polymers and Molecular Clusters: Synthesis and Crystal Structures of [M(Te6)]X3 (M = Rh, Ir; X = Cl, Br, I) and [Ru2(Te6)](TeBr3)4(TeBr2)2
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配位聚合物和分子簇中的六碲环:[M(Te6)]X3(M = Rh、Ir;X = Cl、Br、I)和 [Ru2(Te6)](TeBr3)4(TeBr2) 的合成和晶体结构2

DOI:
10.1002/zaac.201100454
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发表时间:
2012
期刊:
Zeitschrift für anorganische und allgemeine Chemie
影响因子:
--
通讯作者:
M. Ruck
M. Ruck
中科院分区:
--
文献类型:
--
作者:
A. Günther;M. Ruck

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富电子过渡金属M(M= Ru,Rh,Ir)、碲和TeX 4(X= Cl,Br,I)的反应产生了五种三元配位聚合物的黑色晶体,一般组成为MIII(Te 6)X3(M= Rh,Ir)和分子簇化合物RuII 2(Te 6)(TeIIBr 3)4(TeIIBr 2)2。单晶的X射线衍射显示,化合物M(Te 6)X3在三角空间群R <$3 c中同结构结晶。在它们的晶体结构中,线性的带正电荷的MIII(Te 6)链形成六角棒包装的图案。在链中,每个具有椅子构象的形式上不带电荷的Te 6分子作为两个M原子的双三齿桥接配体。八面体配位的M原子是共享杂立方烷片段的反式顶点链中的螺原子。包括提供电荷平衡的孤立卤素离子,整个排列类似于α-钋结构类型的切口。在单斜晶系化合物Ru 2 Te 12 Br 16(空间群P21/n)中,分子簇Ru 2(Te 6)(TeBr 3)4(TeBr 2)2的杂立方烷核的钌原子被末端溴碲酸盐(II)基团饱和。再一次,Te 6环在形式上是不带电的。由于碲原子作为电子对供体,所有化合物中的M原子都满足18电子规则。
The reaction of an electron‐rich transition metal M (M= Ru, Rh, Ir), tellurium and TeX4 (X= Cl, Br, I) resulted in black crystals of five ternary coordination polymers with the general composition MIII (Te6) X3 (M= Rh, Ir) and of the molecular cluster compound RuII2 (Te6)(TeIIBr3) 4 (TeIIBr2) 2. X‐ray diffraction on single‐crystals revealed that the compounds M (Te6) X3 crystallize isostructurally in the trigonal space group type R ̄3 c. In their crystal structures linear, positively charged MIII (Te6) chains form the motif of a hexagonal rod packing. In the chain, each of the formally uncharged Te6 molecules with chair conformation acts as a bis‐tridentate bridging ligand to two M atoms. The octahedrally coordinated M atoms are spiro atoms in the chain of trans vertices sharing heterocubane fragments. Including the isolated halide ions, which provide charge balance, the entire arrangement resembles a cut‐out of the α‐polonium structure type. In the monoclinic compound Ru2Te12Br16 (space group P21/n), the ruthenium atoms of the hetero‐cubane core of the molecular cluster Ru2 (Te6)(TeBr3) 4 (TeBr2) 2 are saturated by terminal bromidotellurate (II) groups. Again, the Te6 ring is formally uncharged. With the tellurium atoms acting as electron‐pair donors the 18 electron rule is fulfilled for the M atoms in all compounds.
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