How electron-deficient Cp ligand facilitates Rh-catalyzed annulations with alkynes

2022 ◽  
Author(s):  
Han Gao ◽  
Lingfei Hu ◽  
Yanlei Hu ◽  
Xiangying Lv ◽  
Yanbo Wu ◽  
...  
Keyword(s):  
Dft Calculations ◽  
Decomposition Analysis ◽  
Energy Decomposition Analysis ◽  
Energy Decomposition ◽  
Ligand Effects

The mechanism and origin of CpX ligand effects on Rh-catalyzed annulations with alkynes were investigated by using DFT calculations and the approach of energy decomposition analysis (EDA). The results reveal...

scholarly journals Benchmarking lithium amide versus amine bonding by charge density and energy decomposition analysis arguments

2018 ◽  
Vol 9 (12) ◽  
pp. 3111-3121 ◽  
Author(s):  
Felix Engelhardt ◽  
Christian Maaß ◽  
Diego M. Andrada ◽  
Regine Herbst-Irmer ◽  
Dietmar Stalke
Keyword(s):  
Quantum Theory ◽  
Dft Calculations ◽  
Charge Density ◽  
Decomposition Analysis ◽  
Atoms In Molecules ◽  
Energy Decomposition Analysis ◽  
Energy Decomposition ◽  
Lithium Amide ◽  
Experimental Charge Density ◽  
Amide Versus

We investigated [{(Me2NCH2)2(C4H2N)}Li]2 (1) by means of experimental charge density calculations based on the quantum theory of atoms in molecules (QTAIM) and DFT calculations using energy decomposition analysis (EDA).

scholarly journals From Intermolecular Interaction Energies and Observable Shifts to Component Contributions and Back Again: A Tale of Variational Energy Decomposition Analysis

2021 ◽  
Vol 72 (1) ◽  
pp. 641-666
Author(s):  
Yuezhi Mao ◽  
Matthias Loipersberger ◽  
Paul R. Horn ◽  
Akshaya Das ◽  
Omar Demerdash ◽  
...  
Keyword(s):  
Dft Calculations ◽  
Intermolecular Interaction ◽  
Density Functional ◽  
Decomposition Analysis ◽  
Radical Cations ◽  
Energy Decomposition Analysis ◽  
Interaction Energies ◽  
Energy Decomposition ◽  
Functional Theory ◽  
Pauli Repulsion

Quantum chemistry in the form of density functional theory (DFT) calculations is a powerful numerical experiment for predicting intermolecular interaction energies. However, no chemical insight is gained in this way beyond predictions of observables. Energy decomposition analysis (EDA) can quantitatively bridge this gap by providing values for the chemical drivers of the interactions, such as permanent electrostatics, Pauli repulsion, dispersion, and charge transfer. These energetic contributions are identified by performing DFT calculations with constraints that disable components of the interaction. This review describes the second-generation version of the absolutely localized molecular orbital EDA (ALMO-EDA-II). The effects of different physical contributions on changes in observables such as structure and vibrational frequencies upon complex formation are characterized via the adiabatic EDA. Example applications include red- versus blue-shifting hydrogen bonds; the bonding and frequency shifts of CO, N2, and BF bound to a [Ru(II)(NH3)5]2 + moiety; and the nature of the strongly bound complexes between pyridine and the benzene and naphthalene radical cations. Additionally, the use of ALMO-EDA-II to benchmark and guide the development of advanced force fields for molecular simulation is illustrated with the recent, very promising, MB-UCB potential.

scholarly journals Looking at the big picture in activation strain model/energy decomposition analysis: the case of the ortho–para regioselectivity rule in Diels–Alder reactions

2020 ◽  
Vol 18 (6) ◽  
pp. 1104-1111 ◽  
Author(s):  
Nicolás Grimblat ◽  
Ariel M. Sarotti
Keyword(s):  
Dft Calculations ◽  
Decomposition Analysis ◽  
Diels Alder ◽  
Energy Decomposition Analysis ◽  
Energy Decomposition ◽  
Big Picture ◽  
Strain Model

The regioselectivity of the DA reaction is predicted by the ortho–para rule which has been explained from FMO theory. Using DFT calculations and ASM/EDA, we found that the results vary depending the position where it is performed.

scholarly journals Probing radical–molecule interactions with a second generation energy decomposition analysis of DFT calculations using absolutely localized molecular orbitals

2020 ◽  
Vol 22 (23) ◽  
pp. 12867-12885
Author(s):  
Yuezhi Mao ◽  
Daniel S. Levine ◽  
Matthias Loipersberger ◽  
Paul R. Horn ◽  
Martin Head-Gordon
Keyword(s):  
Dft Calculations ◽  
Second Generation ◽  
Decomposition Analysis ◽  
Closed Shell ◽  
Energy Decomposition Analysis ◽  
Proper Treatment ◽  
Energy Decomposition ◽  
Localized Molecular Orbitals ◽  
Intermolecular Complexes ◽  
Molecule Interactions

Proper treatment of intermolecular complexes formed by radicals and closed-shell molecules in energy decomposition analysis of DFT calculations.

Remote Metal-Arene π Bonding in Organometallic Complexes: a DFT Study

2007 ◽  
Vol 72 (5-6) ◽  
pp. 703-714 ◽  
Author(s):  
Paulo J. Costa ◽  
Maria José Calhorda ◽  
Paul S. Pregosin
Keyword(s):  
Dft Calculations ◽  
Decomposition Analysis ◽  
Covalent Bond ◽  
Phenyl Group ◽  
Organometallic Complexes ◽  
Dft Study ◽  
Energy Decomposition Analysis ◽  
Coordination Geometry ◽  
Energy Decomposition ◽  
Experimental Parameters

The observation that the 14-electron cation [Rh(PPh3)3]+ is more electron-rich than expected, as a result of coordination of a C=C bond in one phenyl group, opened the way to a search for more examples of this behavior. We used DFT calculations and energy decomposition analysis to study this M-η2-arene interaction and to calculate its strength. For this purpose, we have chosen two formally unsaturated complexes, viz. [Mo(η5-C5H5)(CO)2(PPh3)]+ (1) and [Ru(η5-C5H5)(binap)]+ (2). In the former complex, the PPh3 ligand can be easily moved away from the metal, destroying the Mo-η2-arene interaction, while in 2 this is achieved by a distortion of the Binap ligand. The experimental parameters, namely the distortion of the aryl-containing ligand, have been well reproduced by the calculated coordination geometry; the M-η2-arene interaction was estimated as 13.4 kcal mol-1 for Mo and 21.4 kcal mol-1 for Ru. The energy decomposition analysis revealed the formation of a covalent bond between the metal and the C=C bond, which made the global process favorable, regard- less the energy required to reorganize the geometry of the ligand in the new environment.

scholarly journals A theoretical study on borenium ion affinities toward ammonia, formaldehyde and chloride anions

RSC Advances ◽  
2015 ◽  
Vol 5 (93) ◽  
pp. 75895-75910 ◽  
Author(s):  
Milovan Stojanović ◽  
Marija Baranac-Stojanović
Keyword(s):  
Dft Calculations ◽  
Theoretical Study ◽  
Decomposition Analysis ◽  
Energy Decomposition Analysis ◽  
Energy Decomposition

The effect of R/R′ and L on borenium ion affinities toward NH3, HCHO and Cl− has been evaluated by DFT calculations and rationalized on the basis of an energy decomposition analysis.

scholarly journals DFT Study on the Mechanism of Iron-Catalyzed Diazocarbonylation

Molecules ◽  
2020 ◽  
Vol 25 (24) ◽  
pp. 5860
Author(s):  
Tímea R. Kégl ◽  
László Kollár ◽  
Tamás Kégl
Keyword(s):  
Free Energy ◽  
Dft Calculations ◽  
Reaction Rate ◽  
Decomposition Analysis ◽  
Donor Ligands ◽  
Energy Decomposition Analysis ◽  
Doublet State ◽  
Energy Decomposition ◽  
Natural Orbitals ◽  
Free Energy Of Activation

The mechanism of the carbonylation of diazomethane in the presence of iron–carbonyl–phosphine catalysts has been investigated by means of DFT calculations at the M06/def-TZVP//B97D3/def2-TZVP level of theory, in combination with the SMD solvation method. The reaction rate is determined by the formation of the coordinatively unsaturated doublet-state Fe(CO)3(P) precursor followed by the diazoalkane coordination and the N2 extrusion. The free energy of activation is predicted to be 18.5 and 28.2 kcal/mol for the PF3 and PPh3 containing systems, respectively. Thus, in the presence of less basic P-donor ligands with stronger π-acceptor properties, a significant increase in the reaction rate can be expected. According to energy decomposition analysis combined with natural orbitals of chemical valence (EDA–NOCV) calculations, diazomethane in the Fe(CO)3(phosphine)(η1-CH2N2) adduct reveals a π-donor–π-acceptor type of coordination.

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