16OSTM10: a new open-shell transition metal conformational energy database to challenge contemporary semiempirical and force field methods

Otlyotov, Arseniy A.; Moshchenkov, Andrey D.; Cavallo, Luigi; Minenkov, Yury

doi:10.1039/d2cp01659a

“…Preliminary geometry optimizations were performed using the PBEh-3c method, which is a reparametrized version of PBE0 (with 42% HF exchange) that uses a split-valence double-ζ basis set (def2-mSVP), with ECP on Ru , and adds three corrections considering dispersion, basis set superposition, and other basis set incompleteness effects. − The viability of the PBEh-3c method toward transition-metal complexes was recently highlighted . Further refinement of the structures was carried out with the hybrid meta-GGA DFT functional TPSS0, with 25% HF exchange in combination with Ahlrichs’ def-2 TZVP basis set, with relativistic pseudopotential on Ru. , The C-PCM implicit solvation model was added to all calculations, considering acetone as continuous medium. , IR simulations were carried out using the harmonic approximation, from which zero-point vibrational energies and thermal corrections ( T = 298.15 K) were obtained.…”

Section: Methodsmentioning

confidence: 99%

“… 56 − 58 The viability of the PBEh-3c method toward transition-metal complexes was recently highlighted. 59 Further refinement of the structures was carried out with the hybrid meta-GGA DFT functional TPSS0, 60 with 25% HF exchange in combination with Ahlrichs’ def-2 TZVP basis set, with relativistic pseudopotential on Ru. 54 , 55 The C-PCM implicit solvation model was added to all calculations, considering acetone as continuous medium.…”

Section: Methodsmentioning

confidence: 99%

Triazine Chalcogenones from Thiocyanate or Selenocyanate Addition to Tetrazine Ligands in Ruthenium Arene Complexes

Bonaldi,

Bortoluzzi,

Zacchini

et al. 2023

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The chemistry of 1,2,4,5-tetrazines has attracted considerable interest both from a synthetic and applicative standpoint. Recently, regioselective reactions with alkynes and alkenes have been reported to be favored once the tetrazine ring is coordinated to Re(I), Ru(II), and Ir(III) centers. Aiming to further explore the effects of metal coordination, herein, we unveil the unexplored reactivity of tetrazines with chalcogenocyanate anions. Thus, ruthenium(II) tetrazine complexes, [RuCl{κ2 N-3-(2-pyridyl)-6-R-1,2,4,5-tetrazine}(η6-arene)]+ (arene = p-cymene, R = H, [1a]+, R = Me, [1b]+, R = 2-pyridyl, [1c]+; arene = C6Me6, R = H, [1d]+, R = Me, [1e]+; PF6 – salts), reacted quantitatively and in mild conditions with M(ECN) salts (M = Na, K, Bu4N; E = O, S, Se). The addition of thiocyanate or selenocyanate to the tetrazine ligand is regioselective and afforded, via N2 release, 1,2,4-triazine-5-chalcogenone heterocycles, the one with selenium being unprecedented. The novel ruthenium complexes [RuCl{κ2 N-(2-pyridyl)}{triazine chalcogenone}(η6-arene)] 2a–e (sulfur), 3b, 3d, and 3e (selenium) were characterized by analytical (CHNS analyses, conductivity), spectroscopic (IR, multinuclear and two-dimensional (2D) NMR), and spectrometric (electrospray ionization mass spectrometry (ESI-MS)) techniques. According to density functional theory (DFT) calculations, the nucleophilic attack of SCN– on the tetrazine ring is kinetically driven. Compound 2b is selectively and reversibly mono-protonated on the triazine ring by HCl or other strong acids, affording a single tautomer. When reactions of chalcogenocyanates were performed on the 2,2′-bipyridine (bpy) complex [RuCl(bpy)(η6-p-cymene)]+, the chloride substitution products [Ru(ECN)(bpy)(η6-p-cymene)]+ (E = O, [4]+; E = S, [5]+; E = Se, [6]+) were obtained in 82–90% yields (PF6 – salts). Combined spectroscopic data (IR, 1H/13C/77Se NMR) was revealed to be a useful tool to study the linkage isomerism of the chalcogenocyanate ligand in [4–6]+.

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“…Geometry optimizations were performed using the PBEh-3c method, which is a reparametrized version of PBE0 , (with 42% HF exchange) that uses a split-valence double-zeta basis set (def2-mSVP) , and adds three corrections considering dispersion, basis set superposition, and other basis set incompleteness effects. − The C-PCM implicit solvation model was added to DFT calculations, considering a dielectric constant of 46.68 and a refractive index of 1.4793. , IR simulations were carried out using the harmonic approximation, from which zero-point vibrational energies and thermal corrections ( T = 298.15 K) were obtained . The software used was ORCA version 5.0.3 .…”

Section: Methodsmentioning

confidence: 99%

Highly Reduced Ruthenium Carbide Carbonyl Clusters: Synthesis, Molecular Structure, Reactivity, Electrochemistry, and Computational Investigation of [Ru₆C(CO)₁₅]^4–

Cesari,

Bortoluzzi,

Funaioli

et al. 2023

Inorg. Chem.

2

0

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The reaction of [Ru 6 C(CO) 16 ] 2– ( 1 ) with NaOH in DMSO resulted in the formation of a highly reduced [Ru 6 C(CO) 15 ] 4– ( 2 ), which was readily protonated by acids, such as HBF 4 ·Et 2 O, to [HRu 6 C(CO) 15 ] 3– ( 3 ). Oxidation of 2 with [Cp 2 Fe][PF 6 ] or [C 7 H 7 ][BF 4 ] in CH 3 CN resulted in [Ru 6 C(CO) 15 (CH 3 CN)] 2– ( 5 ), which was quantitatively converted into 1 after exposure to CO atmosphere. The reaction of 2 with a mild methylating agent such as CH 3, I afforded the purported [Ru 6 C(CO) 14 (COCH 3 )] 3– ( 6 ). By employing a stronger reagent, that is, CF 3 SO 3 CH 3 , a mixture of [HRu 6 C(CO) 16 ] − ( 4 ), [H 3 Ru 6 C(CO) 15 ] − ( 7 ), and [Ru 6 C(CO) 15 (CH 3 CNCH 3 )] − ( 8 ) was obtained. The molecular structures of 2–5 , 7 , and 8 were determined by single-crystal X-ray diffraction as their [NEt 4 ] 4 [ 2 ]·CH 3 CN, [NEt 4 ] 3 [ 3 ], [NEt 4 ][ 4 ], [NEt 4 ] 2 [ 5 ], [NEt 4 ][ 7 ], and [NEt 4 ][ 8 ]·solv salts. The carbyne–carbide cluster 6 was partially characterized by IR spectroscopy and ESI-MS, and its structure was computationally predicted using DFT methods. The redox behavior of 2 and 3 was investigated by electrochemical and IR spectroelectrochemical methods. Computational studies were performed in order to unravel structural and thermodynamic aspects of these octahedral Ru–carbide carbonyl clusters...

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“…According to our internal tests, the GFN‐FF demonstrated an unstable performance for some A ± S n systems and this method was ruled out in the present work. The semiempirical methods PM6*/7 were shown in general to be inferior to their GFN n ‐xTB competitors 34–36 …”

Section: Introductionmentioning

confidence: 99%

“…The semiempirical methods PM6*/7 were shown in general to be inferior to their GFNn-xTB competitors. [34][35][36] For these reasons, in the present contribution we examine the performance of the emerging semiempirical GFNn-xTB methods in reproducing conformational energies of singly charged sodium clusters (Na + S n ) with 3 protic (water, methanol, ethanol) and 8 aprotic (formamide, N-methylformamide, dimethylformamide, dimethylacetamide, diethylacetamide, dimethyl sulfoxide, 1,2-dichloroethane, propylene carbonate) solvents. Conformational sampling of these clusters is of crucial importance for detailed comprehension of the Na + solvation process both experimentally 37 and theoretically via the clustercontinuum approach.…”

Section: Introductionmentioning

confidence: 99%

Conformational energies of microsolvated Na⁺ clusters with protic and aprotic solvents from GFNn‐xTB methods

Otlyotov

¹

,

Minenkov

²

2022

Self Cite

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Performance of contemporary tight-binding semiempirical GFNn-xTB methods for the conformational energies of singly charged sodium clusters Na + (S) n (n = 4-8) with 3 protic and 8 aprotic solvents is examined against the reference RI-MP2/CBS method. The median Pearson correlation coefficients of ρ = 0.84 (GFN2-xTB) and ρ = 0.82 (GFN1-xTB) do not give the clear preference to any tested approach. GFN1-xTB method demonstrates more stable performance than its GFN2-xTB successor with the average mean absolute errors (MAEs)/mean signed errors (MSEs) of 1.2/0.2 and 2.3/1.6 kcal mol À1 , respectively. Conformational energies produced by the computationally efficient DFT functional PBE and double-ζ basis set complemented with -D3(BJ) dispersion correction are suitable for the preliminary sampling (median ρ = 0.93), but should be used with a caution for the calculations of the average ensemble properties (MAE/MSE = 1.7/1.1 kcal mol À1 ). Higher-ranking PBE0-D3 (BJ) and ωB97M-V with triple-ζ basis sets yield significantly lower MAEs/MSEs of 0.55/0.20 and 0.51/0.23 kcal mol À1 , respectively.

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16OSTM10: a new open-shell transition metal conformational energy database to challenge contemporary semiempirical and force field methods

Abstract: transition metal (OSTM) complexes has been developed. Contemporary composite density functional theory (DFT) (PBEh-3c, B97-3c), semiempirical (PM6, PM7) and the methods of GFNn-xTB/FF family were examined against conventional DFT (PBE-D3(BJ),...

Cited by 12 publications

References 63 publications

Triazine Chalcogenones from Thiocyanate or Selenocyanate Addition to Tetrazine Ligands in Ruthenium Arene Complexes

Triazine Chalcogenones from Thiocyanate or Selenocyanate Addition to Tetrazine Ligands in Ruthenium Arene Complexes

Highly Reduced Ruthenium Carbide Carbonyl Clusters: Synthesis, Molecular Structure, Reactivity, Electrochemistry, and Computational Investigation of [Ru₆C(CO)₁₅]^4–

Conformational energies of microsolvated Na⁺ clusters with protic and aprotic solvents from GFNn‐xTB methods

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16OSTM10: a new open-shell transition metal conformational energy database to challenge contemporary semiempirical and force field methods

Abstract: transition metal (OSTM) complexes has been developed. Contemporary composite density functional theory (DFT) (PBEh-3c, B97-3c), semiempirical (PM6, PM7) and the methods of GFNn-xTB/FF family were examined against conventional DFT (PBE-D3(BJ),...

Cited by 12 publications

References 63 publications

Triazine Chalcogenones from Thiocyanate or Selenocyanate Addition to Tetrazine Ligands in Ruthenium Arene Complexes

Triazine Chalcogenones from Thiocyanate or Selenocyanate Addition to Tetrazine Ligands in Ruthenium Arene Complexes

Highly Reduced Ruthenium Carbide Carbonyl Clusters: Synthesis, Molecular Structure, Reactivity, Electrochemistry, and Computational Investigation of [Ru6C(CO)15]4–

Conformational energies of microsolvated Na+ clusters with protic and aprotic solvents from GFNn‐xTB methods

Contact Info

Product

Resources

About

Highly Reduced Ruthenium Carbide Carbonyl Clusters: Synthesis, Molecular Structure, Reactivity, Electrochemistry, and Computational Investigation of [Ru₆C(CO)₁₅]^4–

Conformational energies of microsolvated Na⁺ clusters with protic and aprotic solvents from GFNn‐xTB methods