title: Chemistry of transition-metal clusters with mixed Sb/S ligands: evidence for a terminal Sb=S double bond in Cp*3Rh3Sb2S5 (Cp* = C5Me5).
abstract: The reaction of [Cp2*Rh2Cl4] (Cp* = C5Me5) with a slight excess of K(3)SbS(3) 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 1-3 are heterocubane clusters with CpRh, 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) A within the novel mu3-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.
authors.affiliation: Institut für Anorganische Chemie, Universität Regensburg, D-93040 Regensburg, Germany.
authors.forename: Andreas
authors.initials: A
authors.lastname: Lange
authors.forename: Marek M
authors.initials: MM
authors.lastname: Kubicki
authors.forename: Joachim
authors.initials: J
authors.lastname: Wachter
authors.forename: Manfred
authors.initials: M
authors.lastname: Zabel