Abstract
Reaction of Ru 3 (CO) 12 and S(C≡CSiMe 3 ) 2 in toluene gave [Ru 3 (CO) 9 (μ-η 2 -SC≡CSiMe 3 )(μ 3 -η 2 -C≡CSiMe 3 )] 1. The thermolysis of 1 provokes the rupture of the S-C sp bond of the SC≡CSiMe 3 ligand and C-C coupling reactions between two acetylide groups affording the clusters [Ru 3 (CO) 9 (μ 3 -S)(μ 3 -η 2 -C(SiMe 3 )C(C≡CSiMe 3 )] 2, [Ru 2 (CO) 6 -(μ-η 3 -SC≡CSiMe 3 )(μ-η 2 -C≡CSiMe 3 )]3, [Ru 4 (CO) 12 (μ 4 -S)(μ-η 2 -C≡CSiMe 3 ) 2 ] 4 and [Ru 4 (CO) 9 (μ-CO) 2 (μ 4 -S) (μ 4 -η 2 -C(SiMe 3 )C(C≡CSiMe 3 )] 5. All compounds have been characterized by IR and NMR techniques as well as FAB + mass spectrometry. Crystal structures of 1, 4, and 5 have been determined by X-ray diffraction methods. The pathways of the thermolysis of 1 to give 2-5 have been investigated.