Synthesis and desulfurization of 2,5-dihydrothiophene transition-metal complexes: Models for the hydrodesulfurization (HDS) of thiophene
- Iowa State Univ., Ames (United States)
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)[sub 5](2,5-DHT) and Re[sub 2](CO)[sub 9](2,5-DHT) at 110C liberates butadiene and free 2,5-DHT (relative ratio 1:4). Uncoordinated 2,5-DHT itself does not decompose at 120C after 3 days. Thus, S-coordination of 2,5-DHT to these metal centers does promote the liberation of butadiene. Upon being heated at 180C, MCl[sub 2](2,5-DHT)[sub 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 Ru[sub 3](CO)[sub 12] with 2,5-DHT forms the trinuclear ([mu][sub 2]-H)Ru[sub 3](CO)[sub 9]([mu][sub 3]-1-4-[eta][sup 4]-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(PMe[sub 3])[sub 2]Ru(2,5-DHT)](PF[sub 6]) is also reported.
- OSTI ID:
- 6837032
- Journal Information:
- Inorganic Chemistry; (United States), Journal Name: Inorganic Chemistry; (United States) Vol. 30:19; ISSN 0020-1669; ISSN INOCAJ
- Country of Publication:
- United States
- Language:
- English
Similar Records
Synthesis, reactivity, and variable-temperature NMR studies of transition-metal complexes containing the 2,3-dihydrothiophene ligand
Organometallic and reactor studies of the thiophene hydrodesulfurization mechanism
Related Subjects
010402 -- Coal
Lignite
& Peat-- Purification & Upgrading
02 PETROLEUM
020400 -- Petroleum-- Processing
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
CHEMICAL PREPARATION
CHEMICAL REACTIONS
COHERENT SCATTERING
COMPLEXES
DATA
DESULFURIZATION
DIFFRACTION
EXPERIMENTAL DATA
HETEROCYCLIC COMPOUNDS
INFORMATION
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC SULFUR COMPOUNDS
PALLADIUM COMPLEXES
PLATINUM COMPLEXES
POLYCYCLIC SULFUR HETEROCYCLES
RHENIUM COMPLEXES
RUTHENIUM COMPLEXES
SCATTERING
SYNTHESIS
TRANSITION ELEMENT COMPLEXES
TUNGSTEN COMPLEXES
X-RAY DIFFRACTION