Synthesis and reactivity of Ru complexes with dibenzothiophene and hexahydrodibenzothiophene ligands: Models for catalytic hydrodesulfurization.

摘要

As models for the adsorption of dibenzothiophene (DBT) and hexahydrodibenzothiophene (HHDBT) on hydrodesulfurization (HDS) catalysts, the complexes, CpRu(DBT)(sup +), CpRu(HHDBT)(sup +) and ((CpRu)(sub 2)(DBT))(sup 2+), were prepared. In all cases, the metal is bonded to the benzene portion of the ligand in an (eta)(sup 6)-fashion. The reactions of CpRu(DBT)(sup +) with a variety of nucleophiles (H(sup (minus)), CH(sub 3)(sup (minus)), MeO(sup (minus))) give two or four isomers resulting from nucleophilic addition at different carbon atoms of the coordinated benzene ring. These isomers are oxidized back to CpRu(DBT)(sup +), CpRu(HHDBT)(sup +), or their methyl-substituted derivatives upon reaction with electrophiles or oxidizing agents (Ph(sub 3)C(sup +), H(sup +), Me(sub 3)O(sup +), Cp(sub 2)Fe(sup +)). The reaction of M(BEt(sub 3)H) (M = Na or Li) with ((CpRu)(sub 2)(DBT))(sup 2+) results in the formation of the reduced 38-electron dinuclear complex (CpRu)(sub 2)(DBT) and the dihydride adduct (CpRu)(sub 2)(DBT(center dot)2H). An x-ray structure determination of (CpRu)(sub 2)(DBT) shows it to consist of a planar DBT ligand bonded on opposite sides by the two CpRu units. 105 refs., 7 figs., 6 tabs. (ERA citation 15:035200)