Thermochemical stabilities and structures of the cluster ions OCS+, S2+, H+(OCS), and C2H5+ with OCS molecules in the gas phase

Hiraoka, Kenzo; Fujita, Kazuo; Ishida, M; Hiizumi, K.; Nakagawa, Fumiyuki; Wada, Akira; Yamabe, Shinichi; Tsuchida, Noriko

doi:10.1016/j.jasms.2005.07.007

Cited by 8 publications

(6 citation statements)

References 20 publications

(24 reference statements)

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“… a As determined from high pressure mass spectrometry. Refs , , , and . b This value is assigned in the current work to 1 -N 2 (H) and not to the most stable isomer 3 . …”

Section: Introductionmentioning

confidence: 99%

“…C 2 H 5 + -L n clusters, in which the central C 2 H 5 + ion is solvated by a controlled number ( n ) of variable ligands L, are ideal systems to investigate at the molecular level the impact of microsolvation on the structure and reactivity of C 2 H 5 + as a function of the ligand type and the degree of solvation. To this end, early high-pressure mass spectrometric studies on size-selected C 2 H 5 + -L n clusters with L = rare gas (Rg = Ar, Kr, Xe), H 2 , N 2 , CH 4 , CO 2 , and N 2 O demonstrated mainly the formation of weakly bound, unreacted aggregates, with binding enthalpies ranging from ∼7 kJ/mol for L = Ar to ∼50 kJ/mol for L = N 2 O (Table ). − Considerably stronger bonding for L = OCS (105 kJ/mol) has been taken as evidence for substantial covalent bonding to C 2 H 5 + . Although these mass spectrometric studies provide binding energies of the C 2 H 5 + -L adducts, no structural information about the complex and, in particular, about the C 2 H 5 + ion core could be obtained.…”

Section: Introductionmentioning

confidence: 99%

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IR Spectra of C₂H₅⁺-N₂ Isomers: Evidence for Dative Chemical Bonding in the Isolated Ethanediazonium Ion

2011

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The potential energy surface (PES) of C(2)H(5)(+)-N(2) is characterized in detail by infrared photodissociation (IRPD) spectroscopy of mass-selected ions in a quadrupole tandem mass spectrometer and ab initio calculations at the MP2/6-311G(2df,2pd) level. The PES features three nonequivalent minima. Two local minima, 1-N(2)(H) and 1-N(2)(C), are adduct complexes with binding energies of D(0) = 18 and 12 kJ/mol, in which the N(2) ligand is weakly bonded by electrostatic forces to either the acidic proton or the electrophilic carbon atom of the nonclassical C(2)H(5)(+) ion (1), respectively. The global minimum 3 is the ethanediazonium ion, featuring a weak dative bond of D(0) = 38 kJ/mol. This interaction strength is sufficient to switch the C(2)H(5)(+) structure from nonclassical to classical. The 1-N(2)(C) isomer corresponds to the entrance channel complex for addition of N(2) to 1 yielding the product 3. This reaction involves a small barrier of 7 kJ/mol as a result of the rearrangement of the C(2)H(5)(+) ion. The partly rotationally resolved IRPD spectrum of C(2)H(5)(+)-N(2) recorded in the C-H stretch range is dominated by four bands assigned to 3 and one weak transition attributed to 1-N(2)(H). The abundance ratio of 1-N(2)(H) and 3 estimated from the IRPD spectrum as ∼1% is consistent with the calculated free energy difference of 12 kJ/mol. As the ethanediazonium ion escaped previous mass spectrometric detection, the currently accepted value for the ethyl cation affinity of N(2) is revised from -ΔH(0) = 15.5 ± 1.5 to ∼42 kJ/mol. The first experimental identification and characterization of 3 provides a sensitive probe of the electrophilic character and fluxionality of the ethyl cation. Comparison of 3 with related alkanediazonium ions reveals the drastic effect of the size of the alkyl chain on their chemical reactivity, which is relevant in the context of hydrocarbon plasma chemistry of planetary atmospheres and the interstellar medium, as well as alkylation reactions of (bio)organic molecules (e.g., carcinogenesis and mutagenesis of DNA material).

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“… a As determined from high pressure mass spectrometry. Refs , , , and . b This value is assigned in the current work to 1 -N 2 (H) and not to the most stable isomer 3 . …”

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

IR Spectra of C₂H₅⁺-N₂ Isomers: Evidence for Dative Chemical Bonding in the Isolated Ethanediazonium Ion

2011

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“…Spontaneous reactions of carbon disulfide (CS 2 ) or carbonyl sulfide (OCS) in imidazolium acetate solutions are also expected to form 1-butyl-3-imidazolium-2-dithioca rboxylate (BmimCSS) and 1-butyl-3-imidazolium-2-thiocarboxylate (BmimOCS). Such a hypothesis appears reasonable as long-lived carbenes are known to react with CS 2 . ,− This is of particular importance because CS 2 and OCS are both involved in the global cycling of sulfur. − In particular, the OCS molecule is one of the most abundant long-lived sulfur gases trace released into the atmosphere by oceans and by anthropogenic and natural sources, constituting a strong greenhouse gas …”

Section: Introductionmentioning

confidence: 99%

DFT Study of the Reaction Mechanisms of Carbon Dioxide and its Isoelectronic Molecules CS₂ and OCS Dissolved in Pyrrolidinium and Imidazolium Acetate Ionic Liquids

et al. 2016

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The reaction mechanisms of CO2 and its isoelectronic molecules OCS and CS2 dissolved in N-butyl-N-methylpyrrolidinium acetate and in 1-butyl-3-methylimidazolium acetate were investigated by DFT calculations in "gas phase". The analysis of predicted multistep pathways allowed calculating energies of reaction and energy barriers of the processes. The major role played by the acetate anion in the degradation of the solutes CS2 and OCS as well as in the capture of OCS and CO2 by the imidazolium ring is highlighted. In both ionic liquids, this anion governs the conversion of CS2 into OCS and of OCS into CO2 through interatomic S-O exchanges between the anion and the solutes with formation of thioacetate anions. In imidazolium acetate, the selective capture of CS2 and OCS by the imidazolium ring competes with the S-O exchanges. From the calculated values of the energy barriers a basicity scale of the anions is proposed. The (13)C NMR chemical shifts of the predicted adducts were calculated and agree well with the experimental observations. It is argued that the scenario issued from the calculated pathways is shown qualitatively to be independent from the functionals and basis set used, constitute a valuable tool in the understanding of chemical reactions taking place in liquid phase.

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“…27,28 For the (OCS) n + clusters, the thermochemical stability of the (OCS) 2 + dimer ion was studied by using a pulsed electron-beam high-pressure mass spectrometer, and the formation of a semi-covalent bond in the (OCS) 2 + dimer was reported. 34 The OCS anion clusters have been much more investigated than the cation clusters, because the (OCS) n − clusters are homologous systems of (CO 2 ) n − and (CS 2 ) n − , which have complicated but interesting natures of the electronic structure. 16,20,21,33,[35][36][37][38][39][40][41][42][43][44][45] Sanov and coworkers have extensively studied photochemistry and electronic structure of (OCS) n − using photodissociation and photoelectron imaging techniques.…”

Section: Introductionmentioning

confidence: 99%

IR photodissociation spectroscopy of (OCS)n+ and (OCS)n− cluster ions: Similarity and dissimilarity in the structure of CO2, OCS, and CS2 cluster ions

Inokuchi

Ebata

2015

The Journal of Chemical Physics

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Infrared photodissociation (IRPD) spectra of (OCS)n(+) and (OCS)n(-) (n = 2-6) cluster ions are measured in the 1000-2300 cm(-1) region; these clusters show strong CO stretching vibrations in this region. For (OCS)2 +) and (OCS)2(-), we utilize the messenger technique by attaching an Ar atom to measure their IR spectra. The IRPD spectrum of (OCS)2 (+)Ar shows two bands at 2095 and 2120 cm(-1). On the basis of quantum chemical calculations, these bands are assigned to a C2 isomer of (OCS)2 (+), in which an intermolecular semi-covalent bond is formed between the sulfur ends of the two OCS components by the charge resonance interaction, and the positive charge is delocalized over the dimer. The (OCS)n(+) (n = 3-6) cluster ions show a few bands assignable to "solvent" OCS molecules in the 2000-2080 cm(-1) region, in addition to the bands due to the (OCS)2(+) ion core at ∼2090 and ∼2120 cm(-1), suggesting that the dimer ion core is kept in (OCS)3-6(+). For the (OCS)n(-) cluster anions, the IRPD spectra indicate the coexistence of a few isomers with an OCS(-) or (OCS)2(-) anion core over the cluster range of n = 2-6. The (OCS)2(-)Ar anion displays two strong bands at 1674 and 1994 cm(-1). These bands can be assigned to a Cs isomer with an OCS(-) anion core. For the n = 2-4 anions, this OCS(-) anion core form is dominant. In addition to the bands of the OCS(-) core isomer, we found another band at ∼1740 cm(-1), which can be assigned to isomers having an (OCS)2(-) ion core; this dimer core has C2 symmetry and (2)A electronic state. The IRPD spectra of the n = 3-6 anions show two IR bands at ∼1660 and ∼2020 cm(-1). The intensity of the latter component relative to that of the former one becomes stronger and stronger with increasing the size from n = 2 to 4, which corresponds to the increase of "solvent" OCS molecules attached to the OCS(-) ion core, but it suddenly decreases at n = 5 and 6. These IR spectral features of the n = 5 and 6 anions are ascribed to the formation of another (OCS)2(-) ion core having C2v symmetry with (2)B2 electronic state.

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Thermochemical stabilities and structures of the cluster ions OCS⁺, S₂⁺, H⁺(OCS), and C₂H₅⁺ with OCS molecules in the gas phase

Cited by 8 publications

References 20 publications

IR Spectra of C₂H₅⁺-N₂ Isomers: Evidence for Dative Chemical Bonding in the Isolated Ethanediazonium Ion

IR Spectra of C₂H₅⁺-N₂ Isomers: Evidence for Dative Chemical Bonding in the Isolated Ethanediazonium Ion

DFT Study of the Reaction Mechanisms of Carbon Dioxide and its Isoelectronic Molecules CS₂ and OCS Dissolved in Pyrrolidinium and Imidazolium Acetate Ionic Liquids

IR photodissociation spectroscopy of (OCS)n+ and (OCS)n− cluster ions: Similarity and dissimilarity in the structure of CO2, OCS, and CS2 cluster ions

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Thermochemical stabilities and structures of the cluster ions OCS+, S2+, H+(OCS), and C2H5+ with OCS molecules in the gas phase

Cited by 8 publications

References 20 publications

IR Spectra of C2H5+-N2 Isomers: Evidence for Dative Chemical Bonding in the Isolated Ethanediazonium Ion

IR Spectra of C2H5+-N2 Isomers: Evidence for Dative Chemical Bonding in the Isolated Ethanediazonium Ion

DFT Study of the Reaction Mechanisms of Carbon Dioxide and its Isoelectronic Molecules CS2 and OCS Dissolved in Pyrrolidinium and Imidazolium Acetate Ionic Liquids

IR photodissociation spectroscopy of (OCS)n+ and (OCS)n− cluster ions: Similarity and dissimilarity in the structure of CO2, OCS, and CS2 cluster ions

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Thermochemical stabilities and structures of the cluster ions OCS⁺, S₂⁺, H⁺(OCS), and C₂H₅⁺ with OCS molecules in the gas phase

IR Spectra of C₂H₅⁺-N₂ Isomers: Evidence for Dative Chemical Bonding in the Isolated Ethanediazonium Ion

IR Spectra of C₂H₅⁺-N₂ Isomers: Evidence for Dative Chemical Bonding in the Isolated Ethanediazonium Ion

DFT Study of the Reaction Mechanisms of Carbon Dioxide and its Isoelectronic Molecules CS₂ and OCS Dissolved in Pyrrolidinium and Imidazolium Acetate Ionic Liquids