Deuterium exchange of benzo(b)thiophene: Model complex and heterogeneous reactor studies

Journal Article · Thu Sep 01 04:00:00 EDT 1988 · Journal of Catalysis; (USA)

DOI:https://doi.org/10.1016/0021-9517(88)90235-7· OSTI ID:6583551

Huckett, S C; Angelici, R J; Ekman, M E; Schrader, G L ^[1]

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1. Iowa State Univ., Ames (USA)

The complexes (CpRu(BT)){sup +} and (CpRu(3-MeBT)){sup +}, where BT is benzo(b)thiophene and 3-MeBT is its 3-methyl derivative, are models for {pi}-coordination of BT to hydrodesulfurization (HDS) catalysts via the benzene ring. The BT in these complexes undergoes base-catalyzed deuterium exchange, at the 2 and 7 positions; in KOH/CD{sub 3}OD solutions, the exchange follows the rate law: rate = k(Ru complex)(OH{sup {minus}}). The mechanism is proposed to involve rate-determining proton abstraction by OH{sup {minus}} from either (CpRu(BT)){sup +} or (CpRu(BT)){sup +} followed by transfer of D{sup +} from the CD{sub 3}OD solvent to give the deuterated BT complex. Heterogeneous reactor studies of deuterium exchange of BT with D{sub 2} over several HDS catalysts (PbMo{sub 6.2}S{sub 8}, Co{sub 0.25}MoS, and 5% Re/{gamma}-Al{sub 2}O{sub 3}) and {gamma}-Al{sub 2}O{sub 3} indicate that BT is activated to exchange at the 2 and 3 positions over the catalysts. These results suggest that deuterium exchange of BT over HDS catalysts may occur through routes other than those involving BT {pi}-bonding through its benzene ring to the catalyst surface.

• DOE Contract Number: W-7405-ENG-82
• OSTI ID: 6583551
• Journal Information: Journal of Catalysis; (USA), Journal Name: Journal of Catalysis; (USA) Vol. 113:1; ISSN 0021-9517; ISSN JCTLA
• Country of Publication: United States
• Language: English

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