Synthesis and Desulfurization of 2,5-Dihydrothiophene Transition-Metal Complexes: Models for the Hydrodesulfurization (HDS) of Thiophene

Moon Gun Choi, Robert J. Angelici, Lee M. Daniels

Research output: Contribution to journalArticle

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Abstract

Several S-coordinated 2,5-dihydrothiophene (2,5-DHT) transition-metal complexes were synthesized in order to determine whether or not this type of coordination promotes butadiene elimination from the 2,5-DHT ligand, a step proposed in a mechanism for the hydrodesulfurization (HDS) of thiophene. Thermal decomposition of W(CO)5(2,5-DHT) and Re2(CO)9(2,5-DHT) at 110 [formula omited] °C liberates butadiene and free 2,5-DHT (relative ratio 1:4). Uncoordinated 2,5-DHT itself does not decompose at 120 °C after 3 days. Thus, S-coordination of 2,5-DHT to these metal centers does promote the liberation of butadiene. Upon being heated at 180 °C, MCl2(2,5-DHT)2 (M = Pd, Pt) gives off mainly thiophene and free 2,5-DHT (1:1) with only a small amount of butadiene. Thus, depending on the complex either butadiene or thiophene may be evolved. The reaction of Ru3(CO)12 with 2,5-DHT forms the trinuclear (μ2-H)Ru3(CO)93-1-4-η4-DHT), whose X-ray structure determination shows that the sulfur and olefin of the 2,5-DHT coordinate to two different ruthenium atoms but also C-H cleavage occurs at C(2) forming a C-Ru bond. The structure of an S-coordinated DHT complex [Cp(PMe3)2Ru(2,5-DHT)](PF6) is also reported.

Original languageEnglish
Pages (from-to)3647-3651
Number of pages5
JournalInorganic Chemistry
Volume30
Issue number19
DOIs
Publication statusPublished - 1991 Sep 1

Fingerprint

Thiophenes
Hydrodesulfurization
Coordination Complexes
Desulfurization
butadiene
thiophenes
Transition metals
Carbon Monoxide
transition metals
synthesis
Ruthenium
Alkenes
Sulfur
ruthenium
alkenes
thermal decomposition
cleavage
elimination
Pyrolysis
sulfur

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

Cite this

@article{acfcb42d2bbc449eb4e23b4faf552f90,
title = "Synthesis and Desulfurization of 2,5-Dihydrothiophene Transition-Metal Complexes: Models for the Hydrodesulfurization (HDS) of Thiophene",
abstract = "Several S-coordinated 2,5-dihydrothiophene (2,5-DHT) transition-metal complexes were synthesized in order to determine whether or not this type of coordination promotes butadiene elimination from the 2,5-DHT ligand, a step proposed in a mechanism for the hydrodesulfurization (HDS) of thiophene. Thermal decomposition of W(CO)5(2,5-DHT) and Re2(CO)9(2,5-DHT) at 110 [formula omited] °C liberates butadiene and free 2,5-DHT (relative ratio 1:4). Uncoordinated 2,5-DHT itself does not decompose at 120 °C after 3 days. Thus, S-coordination of 2,5-DHT to these metal centers does promote the liberation of butadiene. Upon being heated at 180 °C, MCl2(2,5-DHT)2 (M = Pd, Pt) gives off mainly thiophene and free 2,5-DHT (1:1) with only a small amount of butadiene. Thus, depending on the complex either butadiene or thiophene may be evolved. The reaction of Ru3(CO)12 with 2,5-DHT forms the trinuclear (μ2-H)Ru3(CO)9(μ3-1-4-η4-DHT), whose X-ray structure determination shows that the sulfur and olefin of the 2,5-DHT coordinate to two different ruthenium atoms but also C-H cleavage occurs at C(2) forming a C-Ru bond. The structure of an S-coordinated DHT complex [Cp(PMe3)2Ru(2,5-DHT)](PF6) is also reported.",
author = "Choi, {Moon Gun} and Angelici, {Robert J.} and Daniels, {Lee M.}",
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Synthesis and Desulfurization of 2,5-Dihydrothiophene Transition-Metal Complexes : Models for the Hydrodesulfurization (HDS) of Thiophene. / Choi, Moon Gun; Angelici, Robert J.; Daniels, Lee M.

In: Inorganic Chemistry, Vol. 30, No. 19, 01.09.1991, p. 3647-3651.

Research output: Contribution to journalArticle

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T1 - Synthesis and Desulfurization of 2,5-Dihydrothiophene Transition-Metal Complexes

T2 - Models for the Hydrodesulfurization (HDS) of Thiophene

AU - Choi, Moon Gun

AU - Angelici, Robert J.

AU - Daniels, Lee M.

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AB - Several S-coordinated 2,5-dihydrothiophene (2,5-DHT) transition-metal complexes were synthesized in order to determine whether or not this type of coordination promotes butadiene elimination from the 2,5-DHT ligand, a step proposed in a mechanism for the hydrodesulfurization (HDS) of thiophene. Thermal decomposition of W(CO)5(2,5-DHT) and Re2(CO)9(2,5-DHT) at 110 [formula omited] °C liberates butadiene and free 2,5-DHT (relative ratio 1:4). Uncoordinated 2,5-DHT itself does not decompose at 120 °C after 3 days. Thus, S-coordination of 2,5-DHT to these metal centers does promote the liberation of butadiene. Upon being heated at 180 °C, MCl2(2,5-DHT)2 (M = Pd, Pt) gives off mainly thiophene and free 2,5-DHT (1:1) with only a small amount of butadiene. Thus, depending on the complex either butadiene or thiophene may be evolved. The reaction of Ru3(CO)12 with 2,5-DHT forms the trinuclear (μ2-H)Ru3(CO)9(μ3-1-4-η4-DHT), whose X-ray structure determination shows that the sulfur and olefin of the 2,5-DHT coordinate to two different ruthenium atoms but also C-H cleavage occurs at C(2) forming a C-Ru bond. The structure of an S-coordinated DHT complex [Cp(PMe3)2Ru(2,5-DHT)](PF6) is also reported.

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