114032-47-2Relevant articles and documents
Hydrodesulfurization model complexes: Nucleophilic addition to π-coordinated benzo[b]thiophenes and thiophene
Huckett, Sara C.,Angelici, Robert J.
, p. 1491 - 1500 (2008/10/08)
The π-bound thiophene (T) and benzo[b]thiophene (BT) complexes [CpRu(BT)]+, [Cp*Ir(BT)]2+, and [Cp*Ir(T)]2+, models for the adsorption of thiophenic compounds to hydrodesulfurization (HDS) catalyst surfaces, react with a variety of nucleophiles (H-, MeO-, (MeO2C)2CH-, EtS-, and phosphines). The BT complexes yield the first isolable transition-metal cyclohexadienyl complexes derived from fused ring aromatic ligands; four isomers of each cyclohexadienyl complex are produced. The isomers result from addition at the four carbons on the benzene ring; for the nucleophiles studied, addition occurs preferentially at the carbon closest to the sulfur atom, C7. This isomer of CpRu(BT·H) has been characterized by an X-ray structure determination. The T complex reacts with phosphines to produce [Cp*Ir(η4-T·PR3)]2+. Double nucleophilic addition reactions (H- and MeO-) of [Cp*Ir(BT)]2+ and [Cp*Ir(3-MeBT)]2+ are also discussed. Reaction of either NaBEt3H or Cp2Co with [Cp*Ir(T)]2+ results in a 2e reduction of the Ir complex. On the basis of 1H NMR data and by analogy to related complexes, this product is formulated as Cp*Ir(η4-T).
