Deuterium substitution of thiophenes by D2: catalytic role of a hydrosulfido-bridged molybdenum complex

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

“…Of particular relevance here are her observations that the complex Cp2Mo2(^2-S2)^2-S)2 splits H2 to form Cp2Mo2(^2-SH)2 (μ2-δ)2> i.e., the sulfide ligands may play an active role in homolytic scission of H2, that Cp2Mo2^2-S2CH2)(|A2-SMe)^2-S) + heterolytically splits H2 and that these species are hydrogénation catalysts for a variety of substrates. The complex, Cp2Mo(S2CH2)(SH)(S) + also catalyzes H/D exchange of the α-hydrogens on thiophene, a reaction also observed over C0M0S HDS catalysts (17). The significance of this body of work is that it demonstrates substantial sw//wr-centered reactivity.…”

Molybdenum−Sulfur Dimers as Electrocatalysts for the Production of Hydrogen at Low Overpotentials

“…Cationic derivatives of the molybdenum sulfide dimers have also been found to react with hydrogen , (e.g., reaction 4). The reaction may involve homolytic cleavage through the addition of hydrogen to the LUMO of the molybdenum cation, which has significant sulfur character, pathway a. Alternatively, the reaction could involve the heterolytic cleavage of hydrogen, with the LUMO serving as a hydride acceptor site, and the HOMO, which is an antibonding metal-based δ* orbital with almost no sulfur character, acting as a base, pathway b.…”

Oxidative Substitution of Carbonyl Groups by Halogen or RS• on the Cubane Cluster CpEt2Mo2Co2S4(CO)2: Preparation of 58-VSE Electron-Deficient Clusters as Models for an Organometallic Desulfurization Material

“…The hydrodesulfurization (HDS) of fossil fuels represents a process which is practiced globally on an immense scale . Molybdenum sulfur compounds are important in the desulfurization of organic sulfur compounds and in the HDS catalytic reaction . The commercial HDS catalyst generally consists of a MoS 2 phase promoted by the addition of Co or Ni and is supported on high surface area alumina. , Thus, the preparation of Mo/S compounds as models for the commercial catalyst has been extensive. , The reactions of Mo/Co/S containing clusters, principally Cp‘ 2 Mo 2 Co 2 S 3 (CO) 4 , with organic sulfur compounds have been used to model the reactions which occur with the commercial Co/Mo/S HDS catalyst .…”

“…Molybdenum sulfur compounds are important in the desulfurization of organic sulfur compounds and in the HDS catalytic reaction . The commercial HDS catalyst generally consists of a MoS 2 phase promoted by the addition of Co or Ni and is supported on high surface area alumina. , Thus, the preparation of Mo/S compounds as models for the commercial catalyst has been extensive. , The reactions of Mo/Co/S containing clusters, principally Cp‘ 2 Mo 2 Co 2 S 3 (CO) 4 , with organic sulfur compounds have been used to model the reactions which occur with the commercial Co/Mo/S HDS catalyst . This cluster has been shown to mediate S atom abstraction from organic sulfur compounds with the concomitant formation of the cubane cluster Cp‘ 2 Mo 2 Co 2 S 4 (CO) 2 and the desulfurized organic hydrocarbon. , A detailed kinetic study by Druker and Curtis 7 has shown that the rate-determining step in the desufurization of thiols is the coordination of the thiol to the Cp‘ 2 Mo 2 Co 2 S 3 (CO) 4 cluster and that the sulfur is removed by a C−S bond homolysis reaction.…”