Two-state reactivity in the acetylene cyclotrimerization reaction catalyzed by a single atomic transition-metal ion: The case for V+ and Fe+

Takayanagi, Toshiyuki

doi:10.1016/j.comptc.2022.113682

Cited by 4 publications

(2 citation statements)

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“…Following our previous benchmark quantum chemistry calculations for open-shell transition metal atom systems, [26][27][28] we carried out an unrestricted version of the B3LYP DFT functional with def2-SVPP and def2-TZVP basis sets. To account for the dispersion effects in the B3LYP functional, Grimme's D3 dispersion corrections (DFT-D3) and the Becke-Johnson (BJ) damping function were employed throughout the present calculations [59].…”

Section: Computational Proceduresmentioning

confidence: 99%

“…Through density functional theory (DFT) calculations of the quantum chemical reaction paths, we previously demonstrated that the conversion of the (C 2 H 2 ) 3 -Fe + -L complex to the C 6 H 6 -Fe + -L complex proceeds via transition states, with relatively lower barriers compared to those in the cyclotrimerization of the complexes with the bare iron ion [26][27][28]. It was found that L = (H 2 O) n (n = 8, 10, 12, and 18) clusters as the ligand reduced the number of transition states [26,28]. We also studied the cyclotrimerization of (three) acetylene units catalyzed by Fe + with several ligands, namely, F − , Cl − , OH − , SH − , NC − , NH 3 , H 2 O, cyclopentadienyl anion (Cp − ), CN − , benzene (Bz), and PH 3 [27].…”

Section: Introductionmentioning

confidence: 99%

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Possible Roles of Transition Metal Cations in the Formation of Interstellar Benzene via Catalytic Acetylene Cyclotrimerization

Murakami,

Matsumoto,

Fujihara

et al. 2023

Molecules

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Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous interstellar molecules. However, the formation mechanisms of PAHs and even the simplest cyclic aromatic hydrocarbon, benzene, are not yet fully understood. Recently, we reported the statistical and dynamical properties in the reaction mechanism of Fe+-catalyzed acetylene cyclotrimerization, whereby three acetylene molecules are directly converted to benzene. In this study, we extended our previous work and explored the possible role of the complex of other 3d transition metal cations, TM+ (TM = Sc, Ti, Mn, Co, and Ni), as a catalyst in acetylene cyclotrimerization. Potential energy profiles for bare TM+-catalyst (TM = Sc and Ti), for TM+NC−-catalyst (TM = Sc, Ti, Mn, Co, and Ni), and for TM+-(H2O)8-catalyst (TM = Sc and Ti) systems were obtained using quantum chemistry calculations, including the density functional theory levels. The calculation results show that the scandium and titanium cations act as efficient catalysts in acetylene cyclotrimerization and that reactants, which contain an isolated acetylene and (C2H2)2 bound to a bare (ligated) TM cation (TM = Sc and Ti), can be converted into a benzene–metal–cation product complex without an entrance barrier. We found that the number of electrons in the 3d orbitals of the transition metal cation significantly contributes to the catalytic efficiency in the acetylene cyclotrimerization process. On-the-fly Born–Oppenheimer molecular dynamics (BOMD) simulations of the Ti+-NC− and Ti+-(H2O)8 complexes were also performed to comprehensively understand the nuclear dynamics of the reactions. The computational results suggest that interstellar benzene can be produced via acetylene cyclotrimerization reactions catalyzed by transition metal cation complexes.

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Section: Computational Proceduresmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Possible Roles of Transition Metal Cations in the Formation of Interstellar Benzene via Catalytic Acetylene Cyclotrimerization

Murakami,

Matsumoto,

Fujihara

et al. 2023

Molecules

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The importance of nuclear dynamics in reaction mechanisms of acetylene cyclotrimerization catalyzed by Fe+-compounds

Murakami

Matsumoto

Takayanagi

et al. 2023

Journal of Organometallic Chemistry

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A general method for locating stationary points on the mixed-spin surface of spin-forbidden reaction with multiple spin states

Zhao

Zou

2023

The Journal of Chemical Physics

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Some chemical reactions proceed on multiple potential energy surfaces and are often accompanied by a change in spin multiplicity, being called spin-forbidden reactions, where the spin–orbit coupling (SOC) effects play a crucial role. In order to efficiently investigate spin-forbidden reactions with two spin states, Yang et al. [Phys. Chem. Chem. Phys. 20, 4129–4136 (2018)] proposed a two-state spin-mixing (TSSM) model, where the SOC effects between the two spin states are simulated by a geometry-independent constant. Inspired by the TSSM model, we suggest a multiple-state spin-mixing (MSSM) model in this paper for the general case with any number of spin states, and its analytic first and second derivatives have been developed for locating stationary points on the mixed-spin potential energy surface and estimating thermochemical energies. To demonstrate the performance of the MSSM model, some spin-forbidden reactions involving 5d transition elements are calculated using the density functional theory (DFT), and the results are compared with the two-component relativistic ones. It is found that MSSM DFT and two-component DFT calculations may provide very similar stationary-point information on the lowest mixed-spin/spinor energy surface, including structures, vibrational frequencies, and zero-point energies. For the reactions containing saturated 5d elements, the reaction energies by MSSM DFT and two-component DFT agree very well within 3 kcal/mol. As for the two reactions OsO+ + CH4 → OOs(CH2)+ + H2 and W + CH4 → WCH2 + H2 involving unsaturated 5d elements, MSSM DFT may also yield good reaction energies of similar accuracy but with some counterexamples. Nevertheless, the energies may be remarkably improved by a posteriori single point energy calculations using two-component DFT at the MSSM DFT optimized geometries, and the maximum error of about 1 kcal/mol is almost independent of the SOC constant used. The MSSM method as well as the developed computer program provides an effective utility for studying spin-forbidden reactions.

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Two-state reactivity in the acetylene cyclotrimerization reaction catalyzed by a single atomic transition-metal ion: The case for V+ and Fe+

Cited by 4 publications

References 73 publications

Possible Roles of Transition Metal Cations in the Formation of Interstellar Benzene via Catalytic Acetylene Cyclotrimerization

Possible Roles of Transition Metal Cations in the Formation of Interstellar Benzene via Catalytic Acetylene Cyclotrimerization

The importance of nuclear dynamics in reaction mechanisms of acetylene cyclotrimerization catalyzed by Fe+-compounds

A general method for locating stationary points on the mixed-spin surface of spin-forbidden reaction with multiple spin states

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