Reactions of [Ru3(CO)12] with thiosaccharin: Synthesis and structure of di-, tri-, tetra- and penta-ruthenium complexes containing a thiosaccharinate ligand(s)

Abstract

Reactions of [Ru3(CO)12] with thiosaccharin (tsacH) at different temperatures have been investigated. At 40 °C, the diruthenium complex [Ru2(CO)6(μ-N,S-tsac)2] (1) is produced and whose ruthenium atoms are bridged by two tsac ligands that are oriented in a head-to-tail fashion. When this reaction is carried out at 66 °C, the tri-, tetra- and penta-ruthenium complexes [H2Ru3(CO)7(μ-N,S-tsac)(μ-C,N–C6H4CNSO2)(μ3-S)] (2), [Ru4(CO)12(μ-N,S-tsac)2(μ4-S)] (3) and [H2Ru5(CO)13(μ-N,S-tsac)(μ-C,N–C6H4CNSO2)(μ3-S)(μ4-S)] (4), respectively, are also isolated in addition to 1. The triruthenium complex 2 exhibits an arachno SRu3 polyhedron containing edge-bridging tsac and C6H4CNSO2 ligands. The tetraruthenium complex 3 consists of two [Ru2(CO)6(μ-N,S-tsac)] fragments linked via a μ4-S ligand, while the pentaruthenium complex 4 is composed of individual Ru3 and Ru2 units linked via a μ4-S ligand. At 81 °C, the same reaction furnishes the pentaruthenium complex [HRu5(CO)15(μ-N,S-tsac)(μ5-S)] (5) containing tsac and μ5-S bridging ligands. The molecular structures of the new complexes have been determined by single-crystal X-ray diffraction analyses, and the bonding in each product has been examined by DFT.