Stabilization of decatellurium molecules in isolated and concatenated clusters

Guenther A, Isaeva A, Ruck M (2013)

Publication Type: Journal article

Publication year: 2013

Journal

Zeitschrift für Anorganische und Allgemeine Chemie Wiley

Book Volume: 639

Pages Range: 254-260

Journal Issue: 2

DOI: 10.1002/zaac.201200430

Abstract

Black, shiny crystals of the molecular cluster compounds (Te 10)[M(TeX4)(TeX3)]2 (M/X = Rh/Cl (1), Ir/Br (2)), (Te10)[Ru(TeI4)(TeI2)] 2 (3), (Te10)[M(TeI4)(TeI2)] 2(TeI4)(Te2I2) (M = Rh (4), Ir (5)) as well as the one-dimensional cluster polymer (Te10I 2)[Ir(TeI4)]2(Te4)I2 (6) were synthesized by melting reactions of an electron-rich transition metal M (M = Ru, Rh, Ir) with tellurium and TeX4 (X = Cl, Br, I). X-ray diffraction on single-crystals revealed that the compounds crystallize in the triclinic space group type P1. 4 and 5 show [3+1]-dimensional modulations of their structures. All compounds contain binuclear complexes with central μ-η4:η4-bridging Te10 units and terminal halogenidotellurate(II) groups. Each of the transition metal cations is in a slightly distorted octahedral coordination by six tellurium atoms; the two [MTe6] octahedra share a common edge. With the tellurium atoms acting as electron-pair donors, the 18 electron rule is fulfilled for the electrophilic M atoms. The central tricyclo[5.1.1.13, 5]- decatellurium molecule consists of two ecliptically stacked Te4 rings, which are linked through two tellurium atoms. The symmetric or asymmetric 3c4e bonds along these almost linear bridges are in analogy to polyanionic forms of tellurium, while the tricyclic conformation is stabilized by the strong bonding to the transition-metal cations. Multi-center bonding (3c4e) is also present in the terminal square [Te+IIX4]2- and the T-shaped [Te+IIX3]- groups. The crystal structures of 4 and 5 are organized in layers of (Te10)[M(TeI 4)(TeI2)]2n+ clusters (n ≤ 2) that are quite robust upon oxidation or reduction as shown by molecular calculations. These clusters alternate with incommensurately modulated layers that probably consist of TeI42- anions and a previously unknown Te2I2 molecule. The uncertainty arises primarily from equal scattering powers of I and Te atoms as well as from the known flexibility of the electron count of the Te10 unit. In 6, neutral Te4 rings concatenate (Te10I2)[Ir(TeI 4)]2 clusters into chains, which run parallel to the a axis. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Involved external institutions

Technische Universität Dresden DE Germany (DE)

How to cite

APA:

Guenther, A., Isaeva, A., & Ruck, M. (2013). Stabilization of decatellurium molecules in isolated and concatenated clusters. Zeitschrift für Anorganische und Allgemeine Chemie, 639(2), 254-260. https://doi.org/10.1002/zaac.201200430

MLA:

Guenther, Anja, Anna Isaeva, and Michael Ruck. "Stabilization of decatellurium molecules in isolated and concatenated clusters." Zeitschrift für Anorganische und Allgemeine Chemie 639.2 (2013): 254-260.

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