The Benzo[b]thlophene (BT) Complexes Cp′(CO)2Re(BT)

Models for BT Adsorption on Hydrodesulfurlization Catalysts

Moon-Gun Choi, Robert J. Angelici

Research output: Contribution to journalArticle

53 Citations (Scopus)

Abstract

Benzo[b]thiophene (BT) coordinates in Cp(CO)2Re(BT) as an equilibrium mixture of η1(S) and 2,3-η2 isomers. When the electron density on the Re is increased by replacing Cp (η5-C5H5) with Cp* (η5-C5Me5), the amount of η2 isomer increases. This shift in equilibrium can be readily explained by assuming that the sulfur in BT is an electron donor toward Re, while bonding of the C(2)–C(3) olefinic bond to Re involves an important component of π back-bonding. The intramolecular nature of the isomerization between 1a and 1b was established by the observation that neither 2-MeBT nor PPh3 was incorporated into the [formula omitted]complexes during the time of isomerization. The observed isomerization and the novel (2,3-η2)-BT coordination mode in 1a and 2a provide for the first time a basis for understanding the hydrogenation and initial steps in the hydrodesulfurization of BT on HDS catalysts. 2-and 3-Methylbenzo[b]thiophenes, 2-MeBT and 3-MeBT, are stronger sulfur-donor ligands than BT and therefore form only the η1(S) isomer of the complexes Cp*(CO)2Re(MeBT). The reactions of Cp*(CO)2Re(BT) (1) with Me3O+ and W(CO)5(THF) give the sulfur adducts Cp*(CO)2Re((2,3-η2)-BT•CH3)+ (5) and Cp*(CO)2Re(η2:η(S)-μ2-BT)W(CO)5 (6). An X-ray structural characterization of the η1(S)-bound 3-MeBT complex Cp*(CO)2Re(η1(S)-3-MeBT) (4) is also reported.

Original languageEnglish
Pages (from-to)3328-3334
Number of pages7
JournalOrganometallics
Volume11
Issue number10
DOIs
Publication statusPublished - 1992 Oct 1

Fingerprint

Carbon Monoxide
isomerization
sulfur
isomers
thiophenes
Adsorption
catalysts
Catalysts
adsorption
Isomerization
Sulfur
Isomers
adducts
hydrogenation
ligands
shift
Thiophenes
Hydrodesulfurization
electrons
x rays

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

Cite this

@article{e21d6c767e534e0db25530fda32d9954,
title = "The Benzo[b]thlophene (BT) Complexes Cp′(CO)2Re(BT): Models for BT Adsorption on Hydrodesulfurlization Catalysts",
abstract = "Benzo[b]thiophene (BT) coordinates in Cp(CO)2Re(BT) as an equilibrium mixture of η1(S) and 2,3-η2 isomers. When the electron density on the Re is increased by replacing Cp (η5-C5H5) with Cp* (η5-C5Me5), the amount of η2 isomer increases. This shift in equilibrium can be readily explained by assuming that the sulfur in BT is an electron donor toward Re, while bonding of the C(2)–C(3) olefinic bond to Re involves an important component of π back-bonding. The intramolecular nature of the isomerization between 1a and 1b was established by the observation that neither 2-MeBT nor PPh3 was incorporated into the [formula omitted]complexes during the time of isomerization. The observed isomerization and the novel (2,3-η2)-BT coordination mode in 1a and 2a provide for the first time a basis for understanding the hydrogenation and initial steps in the hydrodesulfurization of BT on HDS catalysts. 2-and 3-Methylbenzo[b]thiophenes, 2-MeBT and 3-MeBT, are stronger sulfur-donor ligands than BT and therefore form only the η1(S) isomer of the complexes Cp*(CO)2Re(MeBT). The reactions of Cp*(CO)2Re(BT) (1) with Me3O+ and W(CO)5(THF) give the sulfur adducts Cp*(CO)2Re((2,3-η2)-BT•CH3)+ (5) and Cp*(CO)2Re(η2:η(S)-μ2-BT)W(CO)5 (6). An X-ray structural characterization of the η1(S)-bound 3-MeBT complex Cp*(CO)2Re(η1(S)-3-MeBT) (4) is also reported.",
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The Benzo[b]thlophene (BT) Complexes Cp′(CO)2Re(BT) : Models for BT Adsorption on Hydrodesulfurlization Catalysts. / Choi, Moon-Gun; Angelici, Robert J.

In: Organometallics, Vol. 11, No. 10, 01.10.1992, p. 3328-3334.

Research output: Contribution to journalArticle

TY - JOUR

T1 - The Benzo[b]thlophene (BT) Complexes Cp′(CO)2Re(BT)

T2 - Models for BT Adsorption on Hydrodesulfurlization Catalysts

AU - Choi, Moon-Gun

AU - Angelici, Robert J.

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N2 - Benzo[b]thiophene (BT) coordinates in Cp(CO)2Re(BT) as an equilibrium mixture of η1(S) and 2,3-η2 isomers. When the electron density on the Re is increased by replacing Cp (η5-C5H5) with Cp* (η5-C5Me5), the amount of η2 isomer increases. This shift in equilibrium can be readily explained by assuming that the sulfur in BT is an electron donor toward Re, while bonding of the C(2)–C(3) olefinic bond to Re involves an important component of π back-bonding. The intramolecular nature of the isomerization between 1a and 1b was established by the observation that neither 2-MeBT nor PPh3 was incorporated into the [formula omitted]complexes during the time of isomerization. The observed isomerization and the novel (2,3-η2)-BT coordination mode in 1a and 2a provide for the first time a basis for understanding the hydrogenation and initial steps in the hydrodesulfurization of BT on HDS catalysts. 2-and 3-Methylbenzo[b]thiophenes, 2-MeBT and 3-MeBT, are stronger sulfur-donor ligands than BT and therefore form only the η1(S) isomer of the complexes Cp*(CO)2Re(MeBT). The reactions of Cp*(CO)2Re(BT) (1) with Me3O+ and W(CO)5(THF) give the sulfur adducts Cp*(CO)2Re((2,3-η2)-BT•CH3)+ (5) and Cp*(CO)2Re(η2:η(S)-μ2-BT)W(CO)5 (6). An X-ray structural characterization of the η1(S)-bound 3-MeBT complex Cp*(CO)2Re(η1(S)-3-MeBT) (4) is also reported.

AB - Benzo[b]thiophene (BT) coordinates in Cp(CO)2Re(BT) as an equilibrium mixture of η1(S) and 2,3-η2 isomers. When the electron density on the Re is increased by replacing Cp (η5-C5H5) with Cp* (η5-C5Me5), the amount of η2 isomer increases. This shift in equilibrium can be readily explained by assuming that the sulfur in BT is an electron donor toward Re, while bonding of the C(2)–C(3) olefinic bond to Re involves an important component of π back-bonding. The intramolecular nature of the isomerization between 1a and 1b was established by the observation that neither 2-MeBT nor PPh3 was incorporated into the [formula omitted]complexes during the time of isomerization. The observed isomerization and the novel (2,3-η2)-BT coordination mode in 1a and 2a provide for the first time a basis for understanding the hydrogenation and initial steps in the hydrodesulfurization of BT on HDS catalysts. 2-and 3-Methylbenzo[b]thiophenes, 2-MeBT and 3-MeBT, are stronger sulfur-donor ligands than BT and therefore form only the η1(S) isomer of the complexes Cp*(CO)2Re(MeBT). The reactions of Cp*(CO)2Re(BT) (1) with Me3O+ and W(CO)5(THF) give the sulfur adducts Cp*(CO)2Re((2,3-η2)-BT•CH3)+ (5) and Cp*(CO)2Re(η2:η(S)-μ2-BT)W(CO)5 (6). An X-ray structural characterization of the η1(S)-bound 3-MeBT complex Cp*(CO)2Re(η1(S)-3-MeBT) (4) is also reported.

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