Activation of C-S Bond Homolysis by Coordination to a Mo/Co/S-Containing Cluster

摘要

The importance of the hydrodesulfurization (HDS) process, practiced on a global scale for removal of sulfur from fossil fuels, has inspired research on the reactivity of organic sulfur compounds with organometallic complexes, single crystals of metals, and supported catalysts. We recently reported that the cluster Cp′_2Mo_2Co_2(μ_3-S)_2(μ_4-S)(CO)_4 (Cp′ = C_5H_4Me) (1) desulfurizes organic sulfur compounds in solution and is also a precursor for a heterogeneous HDS catalyst. Cluster 1 is converted into the cluster Cp′_2Mo_2Co_2(μ_3-S)_4(CO)_2 (2) in the typical desulfurization reaction (eq 1). This communication reports on the mode of coordination of organic thiols and thiolates to cluster 1, the mobility of thiolates bound to the cluster, and the energetics and mechanism of C-S bond cleavage.