Mechanistic Studies Related to the Fischer–Tropsch Hydrocarbon Synthesis and Some Cognate Processes

Maitlis, Peter M.

doi:10.1002/9783527656837.ch12

Cited by 4 publications

(2 citation statements)

References 56 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The Fischer–Tropsch synthesis has been established to be a strategic industrial reaction converting carbon monoxide and dihydrogen into useful hydrocarbons with variable chain lengths, in search for alternatives to petroleum . This process is viable on cobalt, iron, and ruthenium surfaces, and among different mechanistic proposals, a plausible pathway has emerged consisting in the preliminary CO deoxygenation to surface carbide, which is then hydrogenated to give {CH}, {CH 2 }, and {CH 3 } units . One or more of these C 1 species combine together to form an initiating group that, in turn, undergoes sequential coupling with {CH 2 } to grow homologous linear chains.…”

Section: Introductionmentioning

confidence: 99%

Carbon–Carbon Bond Coupling of Vinyl Molecules with an Allenyl Ligand at a Diruthenium Complex

et al. 2022

View full text Add to dashboard Cite

The room-temperature reactions of the diruthenium μ-allenyl complex [Ru 2 Cp 2 (CO) 2 (NCMe){μ-η 1 :η 2 -CHCCMe 2 }]BF 4 , 3-NCMe, with a series of alkenes, RCHCH 2 , afforded the complexes [Ru 2 Cp 2 (CO) 2 {μ-η 3 :η 2 -CH(R)CHC(Me)C(Me)CH 2 }]BF 4 (RPh, 4; 4-C 6 H 4 Me, 5; Me, 6; n Bu, 7; CO 2 Me, 8; and H, 9), containing an uncommon pentacarbon alkenyl-allyl ligand. Cross experiments with deuterated reagents, i.e., [Ru 2 Cp 2 (CO) 2 (NCMe){μ-η 1 :η 2 -CDCCMe 2 }]BF 4 (3b-NCMe) and CD 2 CD(C 6 H 5 ) (styrene-d 3 ), revealed that the formation of 4−9 is initiated by an attack of the alkene to the central carbon of the allenyl moiety, triggering two distinct C−H activation processes. Compounds 4−9 were characterized by analytical and spectroscopic methods and by single-crystal X-ray diffraction in the cases of 4, 7, and 8. Reported here is the clean coupling on a metallic scaffold between two C 2 and C 3 functions invoked in Fischer−Tropsch mechanistic models.

show abstract

Section: Introductionmentioning

confidence: 99%

Carbon–Carbon Bond Coupling of Vinyl Molecules with an Allenyl Ligand at a Diruthenium Complex

et al. 2022

View full text Add to dashboard Cite

show abstract

“…The Fischer–Tropsch (F-T) reaction is a catalytic process that converts CO and H 2 over metals such as cobalt, iron, and ruthenium into hydrocarbons, mainly n -alkanes and α-olefins, as major products. − The reaction is of great practical importance, as it allows the transformation of nonpetroleum carbon resources such as coal, biomass, natural gas, and CO 2 into useful liquid hydrocarbons. Improving the product selectivity has been a major focus of the F-T catalysis research and is believed to be achieved through catalyst improvement based on mechanistic elucidation …”

Section: Introductionmentioning

confidence: 99%

Linear Hydrocarbon Chain Growth from a Molecular Diruthenium Carbide Platform

et al. 2021

View full text Add to dashboard Cite

The formation of linear hydrocarbon chains by sequential coupling of C1 units on the metal surface is the central part of the Fischer–Tropsch (F-T) synthesis. Organometallic complexes have provided numerous models of relevant individual C–C coupling events but have failed to reproduce the complete chain lengthening sequence that transforms a linear C n hydrocarbon chain into its C n+1 homologue in an iterative fashion. In this work, we demonstrate stepwise growth of linear C n hydrocarbon chains and their conversion to their C n+1 homologues via consecutive addition of CH2 units on a molecular diruthenium carbide platform. The chain growth sequence is initiated by the formation of a μ-η1:η1-CCH2 ligand from a C + CH2 coupling between the μ-carbido complex [(Cp*Ru)2(η-NPh)(μ-C)] (1; Cp* = η5-C5Me5) and Ph2SCH2. Then, the chain propagates via a general CCHR + CH2 coupling and subsequent hydrogen-assisted isomerization of the resulting allene ligand μ-η1:η3-H2CCCHR to a higher vinylidene homologue μ-η1:η1-CCH(CH2)R. By repeating this reaction sequence, up to C6 chains have been synthesized in a stepwise fashion. The key step of this chain homologation sequence is the selective hydrogenation of the μ-η1:η3-allene unit to the corresponding μ-alkylidene ligand. Isotope labeling and computational studies indicate that this transformation proceeds via the hydrogenation of the allene ligand to a terminal alkene form and its isomerization to the μ-alkylidene ligand facilitated by the coordinatively unsaturated diruthenium platform.

show abstract

Variation Trends of CO Hydrogenation Performance of (Al)–O–(Zn) Supported Cobalt Nanocomposites: Effects of Gradual Doping with Zn–O Lewis Base

et al. 2016

View full text Add to dashboard Cite

Mechanistic Studies Related to the Fischer–Tropsch Hydrocarbon Synthesis and Some Cognate Processes

Cited by 4 publications

References 56 publications

Carbon–Carbon Bond Coupling of Vinyl Molecules with an Allenyl Ligand at a Diruthenium Complex

Carbon–Carbon Bond Coupling of Vinyl Molecules with an Allenyl Ligand at a Diruthenium Complex

Linear Hydrocarbon Chain Growth from a Molecular Diruthenium Carbide Platform

Variation Trends of CO Hydrogenation Performance of (Al)–O–(Zn) Supported Cobalt Nanocomposites: Effects of Gradual Doping with Zn–O Lewis Base

Contact Info

Product

Resources

About