Covalency in AnCl<sub>3</sub> (An = Th–No)

Cooper, Sophie; Kaltsoyannis, Nikolas

doi:10.1039/d0dt03699d

Cited by 28 publications

(36 citation statements)

References 49 publications

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“…Therefore, care must be taken that the extent of bonding is not strongly dependent on the chosen electronic structure approximations. 83 DFT, with the necessarily approximate functionals that are available, may lead to an incorrect description of actinide−ligand bonding trends. For example, the Kohn−Sham delocalization error (DE) 84 often causes too pronounced ligand-to-metal donation bonding.…”

Section: Introductionmentioning

confidence: 99%

Covalency of Trivalent Actinide Ions with Different Donor Ligands: Do Density Functional and Multiconfigurational Wavefunction Calculations Corroborate the Observed “Breaks”?

Sergentu

Feng

et al. 2021

Inorg. Chem.

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A comprehensive ab initio study of periodic actinide−ligand bonding trends for trivalent actinides is performed. Relativistic density functional theory (DFT) and complete activespace (CAS) self-consistent field wavefunction calculations are used to dissect the chemical bonding in the [AnCl 6 ] 3− , [An-(CN) 6 ] 3− , [An(NCS) 6 ] 3− , [An(S 2 PMe 2 ) 3 ], [An(DPA) 3 ] 3− , and [An(HOPO)] − series of actinide (An = U−Es) complexes. Except for some differences for the early actinide complexes with DPA, bond orders and excess 5f-shell populations from donation bonding show qualitatively similar trends in 5f n active-space CAS vs DFT calculations. The influence of spin−orbit coupling on donation bonding is small for the tested systems. Along the actinide series, chemically soft vs chemically harder ligands exhibit clear differences in bonding trends. There are pronounced changes in the 5f populations when moving from Pu to Am or Cm, which correlate with previously noted "breaks" in chemical trends. Bonding involving 5f becomes very weak beyond Cm/Bk. We propose that Cm(III) is a borderline case among the trivalent actinides that can be meaningfully considered to be involved in ground-state 5f covalent bonding.

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Section: Introductionmentioning

confidence: 99%

Covalency of Trivalent Actinide Ions with Different Donor Ligands: Do Density Functional and Multiconfigurational Wavefunction Calculations Corroborate the Observed “Breaks”?

Sergentu

Feng

et al. 2021

Inorg. Chem.

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“…If this ratio is less than 0.5, then it is expected to covalent bonding. The value between 0.5 and 1.0 indicates partially ionic bond [35]. The values between 0.095 and 0.524 have been obtained for the bonds of the title molecule.…”

Section: Theoretical Analysismentioning

confidence: 89%

“…The negative ratio of the kinetic to potential energy densities, -G(r)/V(r) can also be used to examine bonding character [35,36]. If this ratio is less than 0.5, then it is expected to covalent bonding.…”

Section: Theoretical Analysismentioning

confidence: 99%

Synthesis and Crystal Structure of Benzyl 4-(2-fluoro-4-(trifluoromethyl)phenyl)- 2,6,6-trimethyl-1,4,5,6,7,8-hexahydroquinoline-3-carboxylate and Its DFT Analysis Combined with Bond Order Modeling in Terms of The Bond Critical Point Quantities

Büyükmumcu

Yıldırım

Çetin

et al. 2021

Preprint

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Inflammation is the underlying cause of many diseases such as cardiovascular diseases, cancer and autoimmune diseases. Recently 1,4-dihydropyridine (1,4-DHP) compounds were found effective to reduce inflammation which contributes to development of inflammation associated diseases. Based on these data we synthesized to investigate this type of action of annulated 1,4-DHP molecule, benzyl 4-(2-fluoro-4-(trifluoromethyl)phenyl)-2,6,6-trimethyl-5-oxo-1,4,5,6,7,8-hexahydroquinoline-3-carboxylate and proved the structure of this molecule by IR, 1H-NMR, 13C-NMR, HMRS and X-ray crystallography.X-ray analyses were conducted to find out the exact 3D structure of the mentioned molecule. The molecular structure crystallizes in triclinic space group, P-1, with a = 7.0889(11) Å, b = 12.4861(18) Å, c = 14.338(2) Å, α = 66.899(4)°, β = 89.025(4)°, γ = 85.101(4)° and V = 1162.9(3) Å3. In the title molecule, C27H25F4NO3, the cyclohexene ring is in a sofa conformation and the 1,4-dihydropyridine ring is in a slight boat conformation. In the 2-fluoro phenyl and benzyl rings form a dihedral angle of 13.6(1)°. In the crystal structure stabilized by the intra- and intermolecular N—H···O, C—H···O and C—H···F interactions. The molecules are linked together to form a dimer by N(1)—H(1N) ···O(1)i and C(2)—H(2A) ···O(1)i hydrogen bonds [symmetry code: (i) x+1,y,z ], producing two R12(6) rings.Natural charge, QTAIM, bond order, molecular planarity and molecular surface analyses have been performed on the optimized geometry by DFT. Considering the quantities obtained at the bond critical poins, the chemical bonds are discussed for classification. The correlation between bond critical point quantities and the bond orders based on different definitions have been explored considering different bond order models from the literature. The Laplacian Bond Order (LBO) gives best correlation for four of five bond order models. All the bond order models with an exception of the model with parameter G have approximately same correlation degree for C-C bonds. For C-H bonds, only bond model with parameters of electron density and the principle curvatures for LBO gives relatively good correlation with R2 value of 0.943. The two phenyl rings of the structure have aromaticity comparable to benzene as deduced from QTAIM quantities and molecular planarity metrics. As a result of molecular surface analysis, the mass density, molecular polarity index, v (the measure of charge balance), σ2tot .v (measure of intermolecular interactions) were calculated and compared with literature values.

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“…The electronic structures of the complexes (CpSiMe 3 ) 3 AnSi(NCHMes) 2 ([An–Si] n , An = Th–Am and n = −1, 0, and 1, Figure ) were explored by calculations of Kohn Sham DFT , using the Gaussian 16 program. In general, the PBE0 method can be used to obtain a reliable structure and energy for actinide complexes. , Actinide atoms were treated with the pseudopotential ECP60MWB and the corresponding ECP60MWB-SEG basis set, − which is a reliable method for calculations of actinide complexes. The 6-311G(d) basis set was used for H, C, N, and Si atoms.…”

Section: Introductionmentioning

confidence: 99%

“…In general, the PBE0 method can be used to obtain a reliable structure and energy for actinide complexes. 60,61 Actinide atoms were treated with the pseudopotential ECP60MWB and the corresponding ECP60MWB-SEG basis set, 62−64 which is a reliable method for calculations of actinide complexes. The 6-311G(d) basis set was used for H, C, N, and Si atoms.…”

Section: ■ Introductionmentioning

confidence: 99%

Theoretical Insights into the Actinide–Silicon Bonding Nature and Stability of a Series of Actinide Complexes with Different Oxidation States

Zhang

et al. 2021

Organometallics

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The electronic structures of a series of complexes (CpSiMe 3 ) 3 AnSi(NCHMes) 2 ([An−Si], An = Th−Am) with different oxidation states (OS = II, III, and IV) of actinides were investigated using the relativistic density functional theory to explore the actinide−silicon bonding, which was evaluated based on the analyses of quantum theory of atoms in molecules (QTAIM) and electron localization function (ELF). The An−Si bond length variation for a series of [An−Si] with different oxidation states may be attributed to the synergistic effect of the steric hindrance and the ability of the actinide atom to accept electrons. The value of An− Si Mayer bond order (MBO) decreases across the actinide series with the same oxidation state. The values of An−Si MBO for the [An II −Si] − (An = Th−Pu) are the largest in general among the complexes with three actinide oxidation states, except that for the Am−Si MBO of [Am IV − Si] + is the largest because of more covalent Am−Si bond in the [Am IV −Si] + complex. The An−Si bonds are highly polarized due to lone pair electrons located on the Si 3s orbital. Moreover, the An−Si bonds possess donor−acceptor interactions according to the analyses of QTAIM and ELF. In addition, the binding energies suggest that the tetravalent complexes [An IV −Si] + are thermodynamically accessible, of which [U IV −Si] + and [Pu IV −Si] + are the most preferable. The electron affinity analysis suggests that the reduction reaction of [An III −Si] → [An II −Si] − should become increasingly facile across the actinide series from Th to Am. This work expands the knowledge on the An−Si bonding, especially for the transuranium−silicon bonding, and guides synthesis of the actinide silicon complexes with different oxidation states.

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Covalency in AnCl₃ (An = Th–No)

Abstract: A range of electron density topology- and orbital-based metrics finds evidence for energy degeneracy-driven covalency in the later 5f series.

Cited by 28 publications

References 49 publications

Covalency of Trivalent Actinide Ions with Different Donor Ligands: Do Density Functional and Multiconfigurational Wavefunction Calculations Corroborate the Observed “Breaks”?

Covalency of Trivalent Actinide Ions with Different Donor Ligands: Do Density Functional and Multiconfigurational Wavefunction Calculations Corroborate the Observed “Breaks”?

Synthesis and Crystal Structure of Benzyl 4-(2-fluoro-4-(trifluoromethyl)phenyl)- 2,6,6-trimethyl-1,4,5,6,7,8-hexahydroquinoline-3-carboxylate and Its DFT Analysis Combined with Bond Order Modeling in Terms of The Bond Critical Point Quantities

Theoretical Insights into the Actinide–Silicon Bonding Nature and Stability of a Series of Actinide Complexes with Different Oxidation States

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Covalency in AnCl3 (An = Th–No)

Abstract: A range of electron density topology- and orbital-based metrics finds evidence for energy degeneracy-driven covalency in the later 5f series.

Cited by 28 publications

References 49 publications

Covalency of Trivalent Actinide Ions with Different Donor Ligands: Do Density Functional and Multiconfigurational Wavefunction Calculations Corroborate the Observed “Breaks”?

Covalency of Trivalent Actinide Ions with Different Donor Ligands: Do Density Functional and Multiconfigurational Wavefunction Calculations Corroborate the Observed “Breaks”?

Synthesis and Crystal Structure of Benzyl 4-(2-fluoro-4-(trifluoromethyl)phenyl)- 2,6,6-trimethyl-1,4,5,6,7,8-hexahydroquinoline-3-carboxylate and Its DFT Analysis Combined with Bond Order Modeling in Terms of The Bond Critical Point Quantities

Theoretical Insights into the Actinide–Silicon Bonding Nature and Stability of a Series of Actinide Complexes with Different Oxidation States

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Covalency in AnCl₃ (An = Th–No)