Computational study of An–X bonding (An = Th, U; X = p-block-based ligands) in pyrrolic macrocycle-supported complexes from the quantum theory of atoms in molecules and bond energy decomposition analysis

O’Brien, Kieran T. P.; Kaltsoyannis, Nikolas

doi:10.1039/c6dt04340b

Cited by 12 publications

(6 citation statements)

References 60 publications

(62 reference statements)

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“…The bond strength of four U–E bonds is the trend of U–Si > U–Sn > U–Ge > U–Pb according to the value of bond order. In addition, the delocalization index (δ) can evaluate the bonding nature, which is a measure of bond order. − The values of δ(U–E) are about 0.5, which can also reveal U–E bonds possess a single-bond feature.…”

Section: Molecular and Electronic Structuresmentioning

confidence: 99%

A Theoretical Study on Divalent Heavier Group 14 Complexes as Promising Donor Ligands for Building Uranium–Metal Bonds

Chi

Lan

et al. 2019

Organometallics

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The study of metal−metal bonds is one of the important challenges in organometallic chemistry and of great significance in applied and structural chemistry. We built a series of potential complexes (CpSiMe 3 ) 3 U-E(NCHMes) 2 (E = Si, Ge, Sn, Pb) by constructing two neutral fragments [(CpSiMe 3 ) 3 U] and [E(NCHMes) 2 ] and investigated their structures with scalar-relativistic theoretical calculations. U−E bonds possess highly polarized U−E interactions and also strong donor−acceptor interactions according to the analyses of MO (molecular orbital), natural charge, QTAIM (quantum theory of atoms in molecules), and ELF (electron localization function). Particularly, the four U−E bonds are mainly composed of U 6d orbitals and E ns orbital, which lead to the nature of donor−acceptor interaction between U and E atoms. These bonds are significantly different from the general uranium−transition-metal and uranium−main-group bonds, Moreover, the U−E bond strengths in the (CpSiMe 3 ) 3 U-E(NCHMes) 2 complexes follow the trend of U−Si > U−Sn > U−Ge > U−Pb according to the results of bond orders and EDA (energy decomposed analysis). The binding energies suggest that the four (CpSiMe 3 ) 3 U-E(NCHMes) 2 complexes are thermodynamically accessible. This work indicates that the divalent heavier group 14 complexes are promising donor ligands for building unsupported uranium−metal bonds.

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Section: Molecular and Electronic Structuresmentioning

confidence: 99%

A Theoretical Study on Divalent Heavier Group 14 Complexes as Promising Donor Ligands for Building Uranium–Metal Bonds

Chi

Lan

et al. 2019

Organometallics

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“…51 Previous theoretical studies have identified that QTAIM analysis can provide insightful information on the bonding nature of actinide complexes. 52,53 The calculated QTAIM parameters of M-N and M-O BCPs in the studied systems are listed in Table 4.…”

Section: Chemical Bonding Analyses Of [An-l] à Complexesmentioning

confidence: 99%

Understanding Am³⁺/Cm³⁺separation with H₄TPAEN and its hydrophilic derivatives: a quantum chemical study

Huang

Wang

et al. 2018

Phys. Chem. Chem. Phys.

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Am3+/Cm3+ separation is an extremely hard but important task in nuclear waste treatment. In this study, Am and Cm complexes formed with a back-extraction agent N,N,N',N'-tetrakis[(6-carboxypyridin-2-yl)methyl]ethylene-diamine (H4TPAEN) and its two derivatives with hydrophilic substituents (methoxy and morpholine groups) were investigated using the density functional theory (DFT). The optimized geometrical structures indicated that the Am3+ cation matched better with the cavities of the three studied ligands than Cm3+, and the Am3+ cations were located deeper in the cavities of the ligands. The bond order and quantum theory of atoms in molecules (QTAIM) analyses suggested that ionic interactions dominated An-N and An-O (An = Cm and Am) bonds. However, weak and different extents of partial covalency could also be found in the Am-N and Cm-N bonds. The O donor atoms in the carboxylate groups preferably coordinated with Cm3+ rather than Am3+, whereas the N atoms preferred Am3+. Therefore, the Am3+/Cm3+ selectivity of H4TPAEN and its two hydrophilic derivatives may be ascribed to the competition between the An-N and An-O interactions and the few dissimilarities in their geometrical structures. Based on our calculations, the methoxy and morpholine groups in the two derivatives can serve as electron-donating groups and enhance the strength of the An-NPY bonds (NPY denotes the nitrogen atom of pyridine ring). When compared with the Am-complex, the Cm-complex exhibited significant strength effect, resulting in the relatively lower Am3+/Cm3+ separation ability of the H4TPAEN's hydrophilic derivatives.

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“…The U–Ru bond order of complex 1 is smaller than that of complex 2 , although the U–Ru bond length for the former is shorter than that for the latter. In addition, the values of the delocalization index (DI) − for the four U–Ru bonds are 0.557, 0.576, 0.588, and 0.674, respectively, implying single character.…”

Section: Molecular and Electronic Structuresmentioning

confidence: 99%

A Theoretical Study of Unsupported Uranium–Ruthenium Bonds Based on Tripodal Ligands

Chi

Wang

et al. 2022

Organometallics

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The investigation of metal−metal bonds has greatly promoted the development of structural and applied chemistry, which is also a special and important branch of organometallic chemistry. According to the structurally authenticated [1, Tren TMS U−RuCp(CO) 2 ] complex containing an unsupported U−Ru bond reported in an experiment, we have constructed a series of similar structures, [2, Tren P−iPr 2 U−RuCp(CO) 2 ], [3, Trapen TMS U−RuCp(CO) 2 ] and [4, ( Ad,Me ArO) 3 NU−RuCp(CO) 2 ], with different tripodal ligands and systematically analyzed the nature of U−Ru bonding by using scalar-relativistic quantum chemical calculations. On the basis of the analysis of the localized molecular orbital, the U−Ru bonds are predominantly composed of Ru 4d orbitals and partly U 6d and 5f orbitals, which indicates that the U−Ru bonds are highly polarized. Noticeably, the contribution of U 6d orbitals is smaller than that of U 5f orbitals for complex 4, which probably contributed to the peak U−Ru covalency based on the values of bond order, delocalization index, and quantum theory of atoms in molecules. The carbonyl stretching vibrational frequencies, the molecular orbitals, and the results of energy decomposition analysis indicate that the strength of the U−Ru bond in the four complexes increases in the following order: 2 < 1 < 3 < 4. This reveals that the U−Ru bond strength is sensitive to the tripodal ligands, including the substituent and skeleton. Furthermore, the binding energies indicate that complex 4 is more thermodynamically accessible. This work improves our understanding of the unsupported U−Ru complexes based on the tripodal ligand and is greatly significant for the selection of precursors to construct more stable actinide−metal bonds.

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Computational study of An–X bonding (An = Th, U; X = p-block-based ligands) in pyrrolic macrocycle-supported complexes from the quantum theory of atoms in molecules and bond energy decomposition analysis

Abstract: Good correlations are found between QTAIM BCP and EDA data for a range of Th(iv)- and Th(iii)-p element bonds.

Cited by 12 publications

References 60 publications

A Theoretical Study on Divalent Heavier Group 14 Complexes as Promising Donor Ligands for Building Uranium–Metal Bonds

A Theoretical Study on Divalent Heavier Group 14 Complexes as Promising Donor Ligands for Building Uranium–Metal Bonds

Understanding Am³⁺/Cm³⁺separation with H₄TPAEN and its hydrophilic derivatives: a quantum chemical study

A Theoretical Study of Unsupported Uranium–Ruthenium Bonds Based on Tripodal Ligands

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Computational study of An–X bonding (An = Th, U; X = p-block-based ligands) in pyrrolic macrocycle-supported complexes from the quantum theory of atoms in molecules and bond energy decomposition analysis

Abstract: Good correlations are found between QTAIM BCP and EDA data for a range of Th(iv)- and Th(iii)-p element bonds.

Cited by 12 publications

References 60 publications

A Theoretical Study on Divalent Heavier Group 14 Complexes as Promising Donor Ligands for Building Uranium–Metal Bonds

A Theoretical Study on Divalent Heavier Group 14 Complexes as Promising Donor Ligands for Building Uranium–Metal Bonds

Understanding Am3+/Cm3+separation with H4TPAEN and its hydrophilic derivatives: a quantum chemical study

A Theoretical Study of Unsupported Uranium–Ruthenium Bonds Based on Tripodal Ligands

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Understanding Am³⁺/Cm³⁺separation with H₄TPAEN and its hydrophilic derivatives: a quantum chemical study