Hydrodesulfurization model complexes: nucleophilic addition to. pi. -coordinated benzo(b)thiophenes and thiophene

Journal Article · Fri Jul 01 04:00:00 EDT 1988 · Organometallics; (United States)

DOI:https://doi.org/10.1021/om00097a007· OSTI ID:6947975

Huckett, S C; Angelici, R J

The ..pi..-bound thiophene (T) and benzo(b)thiophene (BT) complexes (CpRu(BT))/sup +/, (Cp*Ir(BT))/sup 2 +/, and (Cp*Ir(T)/sup 2 +/, models for the adsorption of thiophenic compounds to hydrodesulfurization (HDS) catalysts surfaces, react with a variety of nucleophiles (H/sup -/, MeO/sup -/, (MeO/sub 2/C)/sub 2/CH/sup -/, EtS/sup -/, 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 results 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 x H) has been characterized by an X-ray structure determination. The T complex reacts with phosphines to produce (Cp*Ir(eta/sup 4/-T x PR/sub 3/))/sup 2 +/. Double nucleophilic addition reactions (H/sup -/ and MeO/sup -/) of (Cp*Ir(BT))/sup 2 +/ are also discussed. Reaction of either NaBet/sub 3/H or Cp/sub 2/CO with (Cp*Ir(T))/sup 2 +/ results in a 2e reduction of the Ir complex. On the basis of /sup 1/H NMR data and by analogy to related complexes, this product is formulated as Cp*Ir(eta/sup 4/-T).

• Research Organization: Iowa State Univ., Ames (USA)
• DOE Contract Number: W-7405-ENG-82
• OSTI ID: 6947975
• Journal Information: Organometallics; (United States), Journal Name: Organometallics; (United States) Vol. 7:7; ISSN ORGND
• Country of Publication: United States
• Language: English

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AROMATICS
CATALYSTS
CHEMICAL REACTIONS
COHERENT SCATTERING
DATA
DESULFURIZATION
DIFFRACTION
EXPERIMENTAL DATA
HETEROCYCLIC COMPOUNDS
HYDROGEN 1
HYDROGEN ISOTOPES
INFORMATION
ISOTOPES
LIGHT NUCLEI
MAGNETIC RESONANCE
MATHEMATICAL MODELS
NUCLEAR MAGNETIC RESONANCE
NUCLEI
NUMERICAL DATA
ODD-EVEN NUCLEI
ORGANIC COMPOUNDS
ORGANIC SULFUR COMPOUNDS
POLYCYCLIC SULFUR HETEROCYCLES
RESONANCE
SCATTERING
STABLE ISOTOPES
THIOPHENE
X-RAY DIFFRACTION