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Günther, Anja
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article
Hexatellurium rings in coordination polymers and molecular clusters
Abstract
<p>The reaction of an electron-rich transition metal M (M = Ru, Rh, Ir), tellurium and TeX <sub>4</sub> (X = Cl, Br, I) resulted in black crystals of five ternary coordination polymers with the general composition [M <sup>III</sup>(Te <sub>6</sub>)]X <sub>3</sub> (M = Rh, Ir) and of the molecular cluster compound [Ru <sup>II</sup> <sub>2</sub>(Te <sub>6</sub>)](Te <sup>II</sup>Br <sub>3</sub>) <sub>4</sub>(Te <sup>II</sup>Br <sub>2</sub>) <sub>2</sub>. X-ray diffraction on single-crystals revealed that the compounds [M(Te <sub>6</sub>)]X <sub>3</sub> crystallize isostructurally in the trigonal space group type R${3}$c. In their crystal structures linear, positively charged [M <sup>III</sup>(Te <sub>6</sub>)] chains form the motif of a hexagonal rod packing. In the chain, each of the formally uncharged Te <sub>6</sub> 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 Ru <sub>2</sub>Te <sub>12</sub>Br <sub>16</sub> (space group P2 <sub>1</sub>/n), the ruthenium atoms of the hetero-cubane core of the molecular cluster [Ru <sub>2</sub>(Te <sub>6</sub>)](TeBr <sub>3</sub>) <sub>4</sub>(TeBr <sub>2</sub>) <sub>2</sub> are saturated by terminal bromidotellurate(II) groups. Again, the Te <sub>6</sub> 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.</p>