Unprecedented Association of [Mo6Bri7YiBra6]3− Cluster Units and [MoIIIBr6]3− Complexes: Synthesis, Crystal Structures, and Properties of the Double Salts Rb3[Mo6Bri7YiBra6](Rb3[MoBr6])3 (Y=Se, Te)

Kaplan Kirakci; Stéphane Cordier; Christiane Perrin

doi:10.1002/chem.200600101

journal article Aug 03, 2006

Unprecedented Association of [Mo6Bri7YiBra6]3− Cluster Units and [MoIIIBr6]3− Complexes: Synthesis, Crystal Structures, and Properties of the Double Salts Rb3[Mo6Bri7YiBra6](Rb3[MoBr6])3 (Y=Se, Te)

Kaplan Kirakci Stéphane Cordier

Christiane Perrin

Chemistry – A European Journal Vol. 12 No. 24 pp. 6419-6425 · Wiley

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Abstract

AbstractThe double salts Rb3[Mo6Bri7YiBra6](Rb3[MoBr6])3 (Y=Se, Te) result from the partial disproportionation of the Mo6Br12 octahedral‐cluster‐based bromide, in the presence of corresponding chalcogenides and RbBr salt (crystal data: Rb12[MoBr6]3[Mo6Bri7TeiBra6] (1), Pm$\bar 3$m (No. 221), a=12.1558(2) Å, Z=1, R1=0.028; wR2=0.050; Rb12[MoBr6]3[Mo6Bri7SeiBra6] (2), Pm$\bar 3$m, a=12.144(3) Å, Z=1, R1=0.028; wR2=0.050). The structures of 1 and 2 are built up from [MoIIIBr6]3− complexes and [Mo6Bri7YiBra6]3− cluster units characterised by a random distribution of seven bromine and one chalcogen ligands on all the eight inner positions that face cap the Mo6 clusters. Such a distribution implies a static orientational disorder of the [Mo6Bri7YiBra6]3− units around the origin of the unit cell. Close‐packed anionic layers based on [MoIIIBr6]3− complexes and [Mo6Bri7YiBra6]3− cluster units are stacked in the sequence ABC. This arrangement leads to very short BraBra intercluster unit distances of 3.252 Å, much lower than the sum of the van der Waals radii (3.70 Å). The trivalent oxidation state of molybdenum in the Mo complexes and 24 valence electrons per Mo6 cluster have been confirmed by magnetic susceptibility measurements. Salts 1 and 2 constitute the first examples of structurally characterised bromides containing discrete [MoIIIBr6]3− complexes obtained by means of solid‐state synthesis.

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Details

Published: Aug 03, 2006
Vol/Issue: 12(24)
Pages: 6419-6425
License: View

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Cite This Article

Kaplan Kirakci, Stéphane Cordier, Christiane Perrin (2006). Unprecedented Association of [Mo6Bri7YiBra6]3− Cluster Units and [MoIIIBr6]3− Complexes: Synthesis, Crystal Structures, and Properties of the Double Salts Rb3[Mo6Bri7YiBra6](Rb3[MoBr6])3 (Y=Se, Te). Chemistry – A European Journal, 12(24), 6419-6425. https://doi.org/10.1002/chem.200600101

Unprecedented Association of [Mo6Bri7YiBra6]3− Cluster Units and [MoIIIBr6]3− Complexes: Synthesis, Crystal Structures, and Properties of the Double Salts Rb3[Mo6Bri7YiBra6](Rb3[MoBr6])3 (Y=Se, Te)

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