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 language | English |
|---|---|
| Pages (from-to) | 3328-3334 |
| Number of pages | 7 |
| Journal | Organometallics |
| Volume | 11 |
| Issue number | 10 |
| DOIs | |
| Publication status | Published - 1992 Oct 1 |
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All Science Journal Classification (ASJC) codes
- Physical and Theoretical Chemistry
- Organic Chemistry
- Inorganic Chemistry
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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 journal › Article
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.
PY - 1992/10/1
Y1 - 1992/10/1
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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U2 - 10.1021/om00046a035
DO - 10.1021/om00046a035
M3 - Article
VL - 11
SP - 3328
EP - 3334
JO - Organometallics
JF - Organometallics
SN - 0276-7333
IS - 10
ER -