Theoretical study of lanthanide mono cation-mediated C–F bond activation

Matsuda, Aya; Mori, Hirotoshi

doi:10.1016/j.chemphys.2010.12.005

Cited by 10 publications

(7 citation statements)

References 30 publications

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“…Note that Ma et al 32 very recently studied the activation of an N-H bond in ammonia by Ce + at the B3LYP level of theory, also finding a reasonable agreement with CCSD(T) calculations. Similarly, Matsuda et al 31 studied C-F activation by Ln + using B3LYP and CASPT2, and showed a good agreement between the two methods.…”

Section: Potential Energy Surfaces For Ln + + Nh 3 Reactionsmentioning

confidence: 83%

“…Very few theoretical studies have been published on mono-cations of f-block elements in the literature. 27,31,32 Very recently Ma et al studied the insertion of Ce + in the N-H bond of ammonia by using the DFT/B3LYP and CCSD(T) levels of calculation. 32 In the present work, we will be investigating the mechanisms of the chemical reactions of La + , Sm + , Eu + and Gd + with ammonia by means of the DFT, MP2, CCSD(T) and CASSCF/CASPT2 theoretical methods.…”

Section: Introductionmentioning

confidence: 99%

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Reactivity of lanthanoid mono-cations with ammonia: A combined inductively coupled plasma mass spectrometry and computational investigation

Quemet

Vitorge

Cimas

et al. 2013

International Journal of Mass Spectrometry

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The reactivity of La + , Sm + , Eu + and Gd + with NH 3 (g) and ND 3 (g) is studied in the reaction cell of a quadrupole ICP-MS. For Ln + = La + and Gd + , the primary reaction channel is the formation of the LnNH + protonated nitride leading to H 2 elimination. The LnNH(NH 3) + 1-5 ammonia complexes of the Ln protonated nitride are further generated. Sm + and Eu + are much less reactive: the protonated nitride is not detected, and only small amounts of Ln(NH 3) 0-6 + are observed. DFT, MP2, CCSD(T) and CASSCF/CASPT2 calculations are used to explore the potential energy surfaces. For the La + and Gd + ions of f-block elements, the reaction pathways have three steps: first the formation of LnNH 3 + , then the isomerization to HLnNH 2 + , and finally the loss of H 2 associated with the formation of a Ln-N triple bond in the final product LnNH +. On the other hand, Sm + and Eu + are not able to form stable complexes. This was rationalized in terms of energy barriers for the chemical reactions and electronic promotion energies for these Ln + atoms.

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Section: Potential Energy Surfaces For Ln + + Nh 3 Reactionsmentioning

confidence: 83%

Section: Introductionmentioning

confidence: 99%

Reactivity of lanthanoid mono-cations with ammonia: A combined inductively coupled plasma mass spectrometry and computational investigation

Quemet

Vitorge

Cimas

et al. 2013

International Journal of Mass Spectrometry

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“…126,127 A study including the lanthanide ions from Ce + to Yb + showed that the harpoon and insertion mechanisms are feasible for all ions. 128 As proposed by Bohme et al, it is possible that different substrates can prefer different mechanisms. A computational study of the reaction of CH 3 F and C 6 H 5 F with Ce + and Ho + rationalized the higher rate of reaction observed for the fluoroarene by showing that a stabilizing interaction between the arene  system and the metal lowers the transition for the harpoon mechanism.…”

Section: Cationic Metal Ions the Reaction Of Cationic Species With Amentioning

confidence: 97%

Selectivity of C–H Activation and Competition between C–H and C–F Bond Activation at Fluorocarbons

2017

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Partially fluorinated alkanes, arenes, and alkenes can be transformed by a variety of transition metal and lanthanide systems. Although the C-H bond is weaker than the C-F bond regardless of the hybridization of the carbon, the reaction of the C-F bond at the metal is usually more exothermic than the corresponding reaction of the C-H bonds. Both bonds are activated by the metal systems, but the preference for activating these bonds depends on the nature of the hydrocarbon and of the metal system, so that the reaction can be directed exclusively toward C-H or C-F bonds or yield a mixture of products. Additionally, the presence of fluorine differentiates between C-H bonds at different positions resulting in regioselective C-H bond activation; paradoxically, the strongest C-H bond reacts preferentially. The purpose of this review is to describe the field of reactions of partially fluorinated substrates with transition metal atoms, ions, and molecular complexes. The controlling physical properties (thermodynamics and kinetics) are described first, followed by a description of stoichiometric reactions, with the competition between the C-H and C-F activations as focus. A few representative catalytic systems are discussed. The review also highlights the benefit of combining experimental and theoretical studies.

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“…According to our results, the reactions of Pu and Am systems with fluoromethane show a similar mechanism. The Am + reaction mechanism ( Yb, Ce, Nd, Sm, Gd, Dy and Er, with fluoromethane [13]; they concluded that the harpoon mechanism was the suitable one for this reaction. Accordingly, the activation of C-F bond by Pu + and Am + proceeds as shown in scheme 1, denoting that the pure harpoon mechanism is the most suitable one to describe the reaction of An + + CH 3 F with An = Pu, Am.…”

Section: Reaction Mechanismsmentioning

confidence: 99%

“…Experimentally, the study of the reactivity of actinide species towards the activation of strong bonds is difficult to carry out; to our knowledge only some gas phase reactions of lanthanide ions and few actinide ions have been studied by Gibson's group using mass spectrometry techniques Theoretically also, several factors are at the origin of the relatively small number of computational studies, in particular the issue related to the presence of open shells (4f for lanthanides and 5f for the actinides) and that associated to relativistic effects [10], even if it is recognized that lanthanide 4f electrons do not take part in the bonding, contrarily to what was shown for 5f actinide electrons [11]. Thus, the understanding of the activation mechanism of hydrocarbons strong bonds, in particular the C-F and C-H bonds, by lanthanide or actinide monocations, remains a complex task for theoretical chemists and experimentalists [12][13][14]. Among the rare studies, the reactivity of lanthanide ions for activating C-H and C-F bonds and actinide ions for activating C-H and C-C bonding gas phase has received a particular attention since the end of the 90's.…”

Section: Introductionmentioning

confidence: 99%

C F bond breaking by bare actinide monocations in the gas phase: a relativistic DFT study

Kias

Talbi

Elkechai

et al. 2017

Computational and Theoretical Chemistry

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International audienceInvestigations of the CF bond activation by actinide monocation An+ (An = Ac, Th, Pa, U, Np, Pu and Am) are carried out using relativistic density functional theory (DFT) computations. Originally, the aim of the study is to compare the ability of different actinide ions to break strong bonds particularly in the context of accidental radioactive dissemination. The An+ reaction with the fluorinated hydrocarbon CH3F was selected as a representative system in this context. Unexpectedly, the considered An+ were found to react differently. Via linear transit (LT) and intrinsic reaction coordinate (IRC) calculations, three reaction mechanisms for the CF bond activation, leading to the An–F+ formation, were revealed; the first one, i.e. ‘harpoon’ mechanism which was observed in the case of Pu+, Am+, while the second called ‘insertion-elimination’ mechanism concerned the case of Th+, Pa+, U+ and Np+. DFT computations highlight the particular case of the Ac+ system which presents two different mechanisms according to its spin state: a mechanism qualified as ‘harpoon-like’ for the triplet state and an ‘insertion-elimination’ mechanism for the singlet state. The activation barrier for the fluorine elimination from CH3F is weak for all the studied systems, from 0.9 kcal/mol for Th+ to 8.2 kcal/mol for Am+. Th+ is found as the most effective ion to activate the CF bond and a considerable exergonic character (−81.5 kcal/mol) for this reaction is expected. The performed orbital, population and charge analyses permitted to reveal the role of the actinide 7s, 6d and 5f orbitals and of electron transfers during the reaction

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Theoretical study of lanthanide mono cation-mediated C–F bond activation

Cited by 10 publications

References 30 publications

Reactivity of lanthanoid mono-cations with ammonia: A combined inductively coupled plasma mass spectrometry and computational investigation

Reactivity of lanthanoid mono-cations with ammonia: A combined inductively coupled plasma mass spectrometry and computational investigation

Selectivity of C–H Activation and Competition between C–H and C–F Bond Activation at Fluorocarbons

C F bond breaking by bare actinide monocations in the gas phase: a relativistic DFT study

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