ic050493e_si_001.cif (186.25 kB)

Chemistry of Transition-Metal Clusters with Mixed Sb/S Ligands:  Evidence for a Terminal SbS Double Bond in Cp*3Rh3Sb2S5 (Cp* = C5Me5)

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posted on 17.10.2005, 00:00 by Andreas Lange, Marek M. Kubicki, Joachim Wachter, Manfred Zabel
The reaction of [Cp2*Rh2Cl4] (Cp* = C5Me5) with a slight excess of K3SbS3 in boiling THF gave the neutral clusters [Cp*4Rh4S5] (1), [Cp*3Rh3Sb2S5] (2), and after salt metathesis [Cp*3Rh3SbSn]PF6 (3; n = 5 and 6). The structures of 13 are heterocubane clusters with Cp*Rh, S, and Sb vertices but with sulfur inserted into one (1 and 2) or two (3) edges. X-ray diffraction analysis of 2 additionally reveals a very short Sb−S distance of 2.297(1) Å within the novel μ3-Sb2S4 ligand. Density functional theory calculation of the model compounds [SSbS]3-, [HSSbS]2-, and [HSSbH2S]0 provided strong evidence for the existence of a stable terminal SbS double bond in 2.

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