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Titolo:
Methane to methanethiol conversion by FeS+. A combined experimental and theoretical study
Autore:
Barsch, S; Schroder, D; Schwarz, H; Armentrout, PB;
Indirizzi:
Tech Univ Berlin, Inst Organ Chem, D-10623 Berlin, Germany Tech Univ Berlin Berlin Germany D-10623 an Chem, D-10623 Berlin, Germany Univ Utah, Dept Chem, Salt Lake City, UT 84112 USA Univ Utah Salt Lake City UT USA 84112 Chem, Salt Lake City, UT 84112 USA
Titolo Testata:
JOURNAL OF PHYSICAL CHEMISTRY A
fascicolo: 10, volume: 105, anno: 2001,
pagine: 2005 - 2014
SICI:
1089-5639(20010315)105:10<2005:MTMCBF>2.0.ZU;2-D
Fonte:
ISI
Lingua:
ENG
Soggetto:
GAS-PHASE REACTIONS; COLLISION-INDUCED DISSOCIATION; TRANSLATIONAL ENERGY-DEPENDENCE; TRANSITION-METAL CATIONS; GAUSSIAN-BASIS SETS; ELECTRONIC-STRUCTURE; 2-STATE REACTIVITY; ORGANOMETALLIC CHEMISTRY; MOLECULAR CALCULATIONS; BINDING-ENERGIES;
Tipo documento:
Article
Natura:
Periodico
Settore Disciplinare:
Physical, Chemical & Earth Sciences
Citazioni:
90
Recensione:
Indirizzi per estratti:
Indirizzo: Schwarz, H Tech Univ Berlin, Inst Organ Chem, Str 17,Juni 135, D-10623 Berlin, Germany Tech Univ Berlin Str 17,Juni 135 Berlin Germany D-10623 ermany
Citazione:
S. Barsch et al., "Methane to methanethiol conversion by FeS+. A combined experimental and theoretical study", J PHYS CH A, 105(10), 2001, pp. 2005-2014

Abstract

The reaction of FeS+ with methane is examined by guided ion beam mass spectrometry and density functional theory employing the B3LYP/6-311+G* level of theory. For the FeS+/CD4 system examined in the experiments, two major product ions, Fe+ and FeSD+, are observed along with minor channels leading to FeCD3+, FeSCD3+, and FeSCD+. All products are formed in endothermic processes. The measured thresholds for the formations of Fe+ and FeSD+ are compared with computational data as well as literature thermochemistry. In the theoretical approach, two competing reaction mechanisms for the formation ofFe+, concomitant with neutral methanethiol, are investigated and used to interpret the experimental data. The lowest-energy path involves a formal 1,2-addition of H3C-H across the Fe+-S bond to generate a CH3FeSH+ insertion intermediate. This bond activation step involves spin inversion from the sextet to the quartet surface en route to the products. The occurrence of thesecond conceivable pathway resulting in formation of HFeSCH3+ as an intermediate can be ruled out because of the high-energy demand associated with overcoming the insertion barrier along this pathway.

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Documento generato il 04/07/20 alle ore 17:28:24