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

Reactions of [Ru-3(CO)(12)] with thiosaccharin (tsacH) at different temperatures have been investigated. At 40 degrees C, the diruthenium complex [Ru-2(CO)(6)(mu-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 degrees C, the tri-, tetra- and penta-ruthenium complexes [H2Ru3(CO)(7)(mu-N,S-tsac)(mu-C,N-C6H4CNSO2)(mu(3)-S)] (2), [Ru-4(CO)(12)(mu-N,S-tsac)(2)(mu(4)-S)] (3) and [H2Ru5(CO)(13)(mu-N,S-tsac)(mu-C,N-C6H4CNSO2)(mu(3)-S)(mu(4)-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 [Ru-2(CO)(6)(mu-N,S-tsac)] fragments linked via a mu(4)-S ligand, while the pentaruthenium complex 4 is composed of individual Ru-3 and Ru-2 units linked via a mu(4)-S ligand. At 81 degrees C, the same reaction furnishes the pentaruthenium complex [HRu5(CO)(15)(mu-N,S-tsac)(mu(5)-S)] (5) containing tsac and mu(5)-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. (C) 2019 Elsevier B.V. All rights reserved.