Driving Forces in the Sharpless Epoxidation Reaction: A Coupled AIMD/QTAIM Study

Teixeira, Filipe; Mosquera, Ricardo A.; Melo, André; Freire, Cristina; Cordeiro, M. Natália D. S.

doi:10.1021/acs.inorgchem.6b02770

Cited by 11 publications

(10 citation statements)

References 42 publications

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“…The relatively large dispersion of E Mol /n electrons shown in Figure 5a is justifiable by the relatively small impact the iVSCC should have on the potential felt by the electrons in the atomic basins pertaining to the ligands of each TM complex. Although relying on a local adherence to the virial theorem, the negative value of the electronic kinetic energy in the metal basin, −K(M), is a suitable surrogate for contribution of the metal's population to the electronic energy of the molecule, specially when considering general trends in the data 30,40 .…”

Section: Resultsmentioning

confidence: 99%

TMtopo Dataset — Quantum Geometries and Density Topology for 1.1k Transition Metal Complexes

Teixeira

Silva-Santos²,

Cordeiro³

2021

Preprint

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In this work, we report the TMtopo data set containing optimized geometries, quantum calculated properties, and quantum topological descriptors for 1110 first row TM complexes. Properties were computed at the TPSSh/Def2-TZVP level of theory and the quantum topological descriptors were collected under the framework of the Quantum Theory of Atoms in Molecules (QTAIM), including a systematic topological survey of the Laplacian of the electron density, ∇2ρ(r). This survey yielded novel insights on the proliferation of inner Valence Shell Charge Concentrations (iVSCCs, local minima of ∇2ρ(r)) in the metal center, suggesting that their number is determinant for the stabilization of the metal center in a more intense manner than their arrangement opposing each of the metal’s ligands (Inorg. Chem. 2016, 55, 3653). Pairwise representation of the collected properties revealed overall low correlation, although some structure could be perceived in the data (specially when considering the topological features of ∇ 2 ρ(r)). This suggests that the TMtopo data set could be usefully exploited in the data-driven discovery of new TM complexes with interesting properties for applications in as catalysis, opto-electronics and sustainable energy production and storage.

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Section: Resultsmentioning

confidence: 99%

TMtopo Dataset — Quantum Geometries and Density Topology for 1.1k Transition Metal Complexes

Teixeira

Silva-Santos²,

Cordeiro³

2021

Preprint

Self Cite

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“…Figure depicts the TS for the oxygen-transfer reaction between VO(O 2 )(OH) and two olefinic substrates: an alkene (Figure a), and an allylic alcohol (Figure b), together with a representation of the atomic motions associated with the reaction coordinate (i.e., the vibrational mode associated with an imaginary wavenumber), hereafter referred to by ξ. These structures were obtained from a previous study concerning the Sharpless epoxidation process, using the X3LYP functional in conjunction with a mixed basis set of triple-ζ quality. , The vibrational analysis of these TS structures focused on the characterization of the atomic motions along ξ. For this purpose, the lengths for the V–O (3) , V–O (4) , O (3) –O (4) , O (3) –C (7) , and O (3) –C (8) were considered in addition to the internal coordinates generated from the rules explained in the Methodology section.…”

Section: Resultsmentioning

confidence: 99%

“…The fourth and fifth study cases under reported in this work explored the application of VMARD as a way to characterize the motion along the reaction coordinate of the oxygen-transfer step in vanadium-catalyzed epoxidations, and also on different aza-Diels–Alder condensations. Both these studies relied on the data generated in previous studies by the authors. , …”

Section: Computational Detailsmentioning

confidence: 99%

Improving Vibrational Mode Interpretation Using Bayesian Regression

Teixeira

Cordeiro

2018

J. Chem. Theory Comput.

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To streamline the interpretation of vibrational spectra, this work introduces the use of Bayesian linear regression with automatic relevance determination as a viable approach to decompose the atomic motions along any vibrational mode as a weighted combination of displacements along chemically meaningful internal coordinates. This novel approach denominated vibrational mode automatic relevance determination (VMARD) is presented and compared with the well-established potential energy decomposition (PED) scheme. Good agreement is generally attained between the two methods. VMARD returns a decomposition of the atomic displacement using only a small number of internal coordinates, thus aiding the interpretation of the vibrational spectra. Moreover, the results show that the VMARD descriptions are resilient toward the addition of additional internal coordinates, achieving a concise description of the vibrational modes despite the use of redundant internal coordinates. Potential applications of VMARD involving the gathering of physical insights on the atomic motions along the reaction coordinate at transition state structures, as well as the improvement of theoretically predicted vibrational frequencies, are also presented under a proof-ofconcept perspective.

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“…This method of wave function analysis enables the recovery of important chemical concepts, such as atoms, functional groups, atomic charges, and bond orders from either electronic structure calculations or X-ray experiments [ 44 ]. Consequently, QTAIM has been applied in the study of a wide variety of chemical and physical problems, such as the examination of different bonds [ 45 , 46 ], adsorption [ 47 , 48 , 49 ], electrical conductivity [ 50 , 51 , 52 ], and catalysis [ 53 , 54 , 55 ].…”

Section: Theoretical Frameworkmentioning

confidence: 99%

On the Relationship between Hydrogen Bond Strength and the Formation Energy in Resonance-Assisted Hydrogen Bonds

et al. 2021

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Resonance-assisted hydrogen bonds (RAHB) are intramolecular contacts that are characterised by being particularly energetic. This fact is often attributed to the delocalisation of π electrons in the system. In the present article, we assess this thesis via the examination of the effect of electron-withdrawing and electron-donating groups, namely −F, −Cl, −Br, −CF3, −N(CH3)2, −OCH3, −NHCOCH3 on the strength of the RAHB in malondialdehyde by using the Quantum Theory of Atoms in Molecules (QTAIM) and the Interacting Quantum Atoms (IQA) analyses. We show that the influence of the investigated substituents on the strength of the investigated RAHBs depends largely on its position within the π skeleton. We also examine the relationship between the formation energy of the RAHB and the hydrogen bond interaction energy as defined by the IQA method of wave function analysis. We demonstrate that these substituents can have different effects on the formation and interaction energies, casting doubts regarding the use of different parameters as indicators of the RAHB formation energies. Finally, we also demonstrate how the energy density can offer an estimation of the IQA interaction energy, and therefore of the HB strength, at a reduced computational cost for these important interactions. We expected that the results reported herein will provide a valuable understanding in the assessment of the energetics of RAHB and other intramolecular interactions.

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Driving Forces in the Sharpless Epoxidation Reaction: A Coupled AIMD/QTAIM Study

Cited by 11 publications

References 42 publications

TMtopo Dataset — Quantum Geometries and Density Topology for 1.1k Transition Metal Complexes

TMtopo Dataset — Quantum Geometries and Density Topology for 1.1k Transition Metal Complexes

Improving Vibrational Mode Interpretation Using Bayesian Regression

On the Relationship between Hydrogen Bond Strength and the Formation Energy in Resonance-Assisted Hydrogen Bonds

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