Novel hexanuclear ruthenium clusters with unusual metal framework geometries: ‘boat’ and ‘sofa’ configurations of the Ru 6 core

The thermal reaction of [Ru3(CO)12] with the thioureas SC(NHR)2(R = Et or Ph) in tetrahydrofuran at 130 °C has been studied. With the ethyl substituent, the hexanuclear cluster [Ru6(CO)14(µ-CO)2(µ4-S)(µ3-η2-EtNCSNHEt)(µ3-η2-EtNCNHEt)] has been isolated and structurally characterized: the molecule presents an unusual Ru6 framework analogous to the boat conformation of cyclohexane. With the phenyl substituent, another hexanuclear cluster [Ru6(CO)16(µ-H)(µ5-S)(µ3-η2-PhNCSNHPh)] has been isolated, the molecular structure of which reveals a previously unreported Ru6 metal core reminiscent of the sofa conformation of cyclohexane.