Protonated MF3 (M=N–Bi): Structure, stability, and thermochemistry of the H–MF3+ and HF–MF2+ isomers

Giordani, Maria; Grandinetti, Felice

doi:10.1016/j.jfluchem.2009.03.008

Cited by 7 publications

(6 citation statements)

References 33 publications

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“…Arsenic fluoride and arsenic chloride are widely used in semiconductor industry as fluorinating/chlorinating agents, dopants, various reagents, strong Lewis acids, nonaquous solvents, etc. Michalska et al [6] studied metal triiodides, while structure, stability and thermochemistry of protonated metal fluorides including arsenic fluoride were studied theoretically by Grandinetti et al [7]. Schaefer et al [8] reported the structures, thermochemistry and electron affinities of a wide range of arsenic fluorides.…”

Section: Introductionmentioning

confidence: 99%

Arsine and its fluoro, chloro derivatives: a computational thermochemical study

et al. 2010

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The structures, vibrational frequencies, enthalpies of formation and dissociation energies of arsine, arsenic hydrides and their fluoro, chloro derivatives have been studied using density functional B3LYP/cc-pVDZ, ab-initio MP2/cc-pVDZ and composite CBS-QB3 and CBS-Q methods. Computed standard enthalpies of formation at 298 K by atomisation scheme are compared with reported values. Bond dissociation energies at 0 K are calculated for all possible thermal dissociation of the molecular species in gas phase, from which the energetically most favourable dissociation pathways are predicted. The calculated enthalpies of formation and bond dissociation energies are correlated with the nature of bonding in arsine and its fluoro, chloro derivatives. Energy barriers at 0 K are calculated and transition states are located for the molecular fragment elimination of the thermal dissociation reactions.

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Section: Introductionmentioning

confidence: 99%

Arsine and its fluoro, chloro derivatives: a computational thermochemical study

et al. 2010

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“…Several previously published studies − show that NF 3 acts as a Lewis base that interacts with electrophilic species through the N and F atoms. Therefore, we explored the attack of GeH 3 on both atoms, and located the energy minima 1 and 2 and the transition states TS_1 and TS_2 shown in Figures and .…”

Section: Computational Resultsmentioning

confidence: 97%

Experimental and Theoretical Study on the Gas-Phase Reactions of Germyl Radicals with NF₃: Homolytic Substitution at the Nitrogen Atom vs Fluorine Abstraction

et al. 2020

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In this paper, we report on the unexplored reaction mechanisms of bimolecular homolytic substitution (S H 2) between GeH 3 radicals and the nitrogen atom of NF 3 . The S H 2 reactions are studied both experimentally and theoretically with ab initio and density functional theory (DFT) calculations. The experimental results of X-ray irradiation of mixtures of GeH 4 and NF 3 show the formation of GeH 3 −NF 2 and GeH 3 −F. The trend of product yields as a function of the increase in GeH 4 partial pressure in the irradiated mixtures evidences the predominant role of GeH 3 radicals. Particularly, the S H 2 mechanism can be hypothesized for the reaction between GeH 3 radicals and NF 3 molecules leading to GeH 3 −NF 2 . This mechanism is further confirmed by the increase in GeH 3 −NF 2 yield observed if O 2 is added, as a radical scavenger, to the reaction mixture. In agreement with the experimental data, from the calculations performed at the CCSD(T) and G3B3 levels of theory, we observe that the GeH 3 − NF 2 product actually occurs from a bimolecular homolytic substitution by the GeH 3 radical, which attacks the N atom of NF 3 , and this reaction is in competition with the fluorine abstraction reaction leading to GeH 3 F, even if other mechanisms may be involved in the formation of this product.

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“…It is well known from previous studies [63][64][65][66][67][68][69][70] that, in the gas phase, NF 3 behaves as a bifunctional Lewis base, being able to interact with electrophilic species by both the N-and the F atom(s). Consistently, the interaction between SiH þ and NF 3 leads to the nitrogen-coordinated isomer 1 and to the two fluorine-coordinated isomers 2a and 2b, that differ for the orientation of the H atom with respect to the ANF 2 moiety.…”

Section: Resultsmentioning

confidence: 99%

Gas‐phase reactions of SiH_n⁺ (n = 1,2) with NF₃: A computational investigation on the detailed mechanistic aspects

et al. 2012

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The mechanism of the gas-phase reactions of SiH(n)(+) (n = 1,2) with NF(3) were investigated by ab initio calculations at the MP2 and CAS-MCSCF level of theory. In the reaction of SiH(+), the kinetically relevant intermediates are the two isomeric forms of fluorine-coordinated intermediate HSi-F-NF(2)(+). These species arise from the exoergic attack of SiH(+) to one of the F atoms of NF(3) and undergo two competitive processes, namely an isomerization and subsequent dissociation into SiF(+) + HNF(2) , and a singlet-triplet crossing so to form the spin-forbidden products HSiF(+) + NF(2). The reaction of SiH(2)(+) with NF(3) involves instead the concomitant formation of the nitrogen-coordinated complex H(2)Si-NF(3)(+) and of the fluorine-coordinated complex H(2)Si-F-NF(2)(+). The latter isomer directly dissociates into NF(2)(+) + H(2)SiF, whereas the former species preferably undergoes the passage through a conical intersection point so to form a H(2) SiF-NF(2)(+) isomer, which eventually dissociates into H(2)SiF(+) and NF(2).

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Protonated MF3 (M=N–Bi): Structure, stability, and thermochemistry of the H–MF3+ and HF–MF2+ isomers

Cited by 7 publications

References 33 publications

Arsine and its fluoro, chloro derivatives: a computational thermochemical study

Arsine and its fluoro, chloro derivatives: a computational thermochemical study

Experimental and Theoretical Study on the Gas-Phase Reactions of Germyl Radicals with NF₃: Homolytic Substitution at the Nitrogen Atom vs Fluorine Abstraction

Gas‐phase reactions of SiH_n⁺ (n = 1,2) with NF₃: A computational investigation on the detailed mechanistic aspects

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Protonated MF3 (M=N–Bi): Structure, stability, and thermochemistry of the H–MF3+ and HF–MF2+ isomers

Cited by 7 publications

References 33 publications

Arsine and its fluoro, chloro derivatives: a computational thermochemical study

Arsine and its fluoro, chloro derivatives: a computational thermochemical study

Experimental and Theoretical Study on the Gas-Phase Reactions of Germyl Radicals with NF3: Homolytic Substitution at the Nitrogen Atom vs Fluorine Abstraction

Gas‐phase reactions of SiHn+ (n = 1,2) with NF3: A computational investigation on the detailed mechanistic aspects

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Experimental and Theoretical Study on the Gas-Phase Reactions of Germyl Radicals with NF₃: Homolytic Substitution at the Nitrogen Atom vs Fluorine Abstraction

Gas‐phase reactions of SiH_n⁺ (n = 1,2) with NF₃: A computational investigation on the detailed mechanistic aspects