Formation of butenethiolate by the ring opening of tetrahydrothiophene by a triosmium cluster complex

Hydrodesulfurization Catalysts and Catalyst Models Based on Mo—Co—S Clusters and Exfoliated MoS2

“…The identity of the anionic, paramagnetic cluster 8 was established unambiguously by preparing it from the one-electron reduction of cubane 2 and structurally characterizing the anion (62). Adams et al have previously observed homolytic C-S bond scission in the reactions of thiols and thietanes with OS3 clusters (45,47,67). In these reactions, multi-point bonding of the thiolate to the cluster is also observed, so that the mechanism of C-S bond activation proposed here applies to the OS3 cluster-mediated reactions as well.…”

“…Adams et al have studied the reactions of organic sulfides with osmium clusters (45)(46)(47). In an extensive series of papers, they have isolated new clusters resulting from S-H, C-S, and C-H bond insertions, as well as reductive elimination of alkanes or arenes, dehydrogenation of the organic moiety and oligomerization of the organic sulfide.…”

Decarbonylation Reaction of [Os3(CO)10(μ-H)(μ-SN2C4H5)]: X-ray Structures of the Two Isomers of [Os3(CO)9(μ-H)(μ 3-η 2-SN2C4H5)]

“…Trinuclear osmium clusters have proved to be useful system for modeling heterogeneous catalytic processes such as hydrodesulfurization (HDS) and hydrodenitrogenation (HDN) which are associated with the cleavage of C-X bonds (X = S, N). 1,2,3,4,5,6,7,8,10,12,13,19,20,21,22,23 The presence of heteroatom's such as sulfur 24,25,26 and nitrogen 27,28,29 not only stabilizes the metal cluster framework with respect to degradational fragmentation in drastic conditions but also provide new types of reactivities and increase the coordination potential towards multi-metal centers. Many of the resultant complexes are biologically important as they can be used as models for metal-centers in metalloproteins 30,31,32,33,34 and also possess different industrial applications such as anticorrosion and as accelerators in the rubber vulcanization process.…”

P–C and C–H bond cleavages of dppm in the thermal reaction of [Ru3(CO)10(μ-dppm)] with benzothiophene: X-ray structures of [Ru6(μ-CO)(CO)13{μ4-PhP(C6H4)PPh}(μ6-C)] and [Ru4(CO)9(μ3-η2-PhPCH2PPh2)(μ4-η6:η1:η1-C6H4)(μ-H)]

“…During the past decade, considerable attention has been devoted to the synthesis and reactivity of osmium and ruthenium carbonyl clusters bearing sulfur-containing ligands such as thiophene, benzothiophene and dibenzothiophene which are common sulfur containing contaminants in petroleum feedstocks [1][2][3][4][5][6][7]. Of these sulfur-containing molecules, benzothiophene is of particular interest because its alkylated derivatives are more difficult to desulfurize than thiophene itself.…”