Preparation of Incomplete Cubane-Type Ru2M(μ3-S)(μ2-Cl)3 Clusters (M = Sb, Bi) and Isolation of the Ru2Sb Cluster Having a Novel μ3-SO Ligand. Functions in Oxygen Atom Transfer and Catalytic Oxidation of PPh3 to O=PPh3 by Molecular O2

Cubane-type clusters containing Ru and group 15 metal [((CpRuCl)-Ru-boolean AND)(2)(mu-SMCl2)(2)] (2a, M = Bi; 2b, M = Sb; CP boolean AND = eta(5)-C5EtMe4) reacted with O-2 gas (1 atm) in 1,2-dichloroethane (DCE) at 60 degrees C to give [((CpRuCl)-Ru-boolean AND)(2)(mu-SBiCl2)(mu-Cl)] (3a) for M = a; and [((CpRuCl)-Ru-boolean AND)2(mu-SOSbCl2)(mu-Cl)] (413) for M = Sb, respectively. The latter cluster, consisting of an SO ligand with the novel mu(3)-(KS)-S-2:kO binding mode, was treated with PPh3 in CH2Cl2 at room temperature to be converted into [((CpRuCl)-Ru-boolean AND)(2)(mu-SSbCl2)(mu-Cl)] (3b) with concurrent generation of O=PPh3. It has been demonstrated that 3b catalyzes the oxidation of PPh3 into O=PPh3 in DCE at 60 C under 02 (1 atm). Similar activity as the catalyst for oxygenation of PPh3 by 02 has also been observed for 3a. An X-ray diffraction study was undertaken to determine the detailed structures for 3a,b and 4b.