Arene binding affinities in [CpRu(eta(6)-arene)](+) complexes: Models for the adsorption of arenes on hydrodesulfurization catalysts
|Title||Arene binding affinities in [CpRu(eta(6)-arene)](+) complexes: Models for the adsorption of arenes on hydrodesulfurization catalysts|
|Publication Type||Journal Article|
|Year of Publication||2008|
|Authors||Choi MG, Ho TC, Angelici RJ|
|Type of Article||Article|
|Keywords||crystal-structure, DIESEL FUELS, DISPLACEMENT-REACTIONS, LIGAND-EXCHANGE, METAL-COMPLEXES, MOLECULAR STRUCTURE, NITROGEN-COMPOUNDS, SELECTIVE ADSORPTION, SULFUR-COORDINATED THIOPHENES, ULTRA-DEEP DESULFURIZATION|
Product/reactant ratios (Y) were determined for the reactions CpRu(eta(6)-DBT)(+) + L reversible arrow CpRu(eta(6)-L)(+) + DBT (where DBT is dibenzothiophene and L is a homo- or heterocyclic arene), which were conducted under UV photolysis conditions. In the photostationary state, the Y values for the different arenes decrease in the following order: mesitylene (17) > toluene (13) > indole (9.1) > carbazole (6.7) > benzene (5.9) > fluorene (5.1) > biphenyl (3.9) > DBT (1.0) > phenanthrene (0.65) > naphthalene (0.35). In general, alkyl-substituted arenes have a higher binding affinity than the parent arene, except for tert-butyl groups, which decrease the Y values. These trends in eta(6)-arene binding to CpRu+ provide a basis for understanding competitive adsorption of arenes on metal sites of hydrotreating catalysts. Such arene components in petroleum feedstocks reduce the rates of hydrodesulfurization of dibenzothiophenes.