scholarly journals Structural Analysis and Reactivity of Tetramethylcopper(III) Complex towards Nitrogen Donor Ligands by Density Functional Theory

2016 ◽  
Vol 2016 ◽  
pp. 1-8
Author(s):  
Perumal Balu ◽  
Venu Kannappan ◽  
Rathinavelu Kumar
Keyword(s):  
Density Functional ◽  
Structural Parameters ◽  
Population Analysis ◽  
Model Systems ◽  
Basis Set ◽  
Donor Ligands ◽  
Energy Decomposition Analysis ◽  
Chemical Hardness ◽  
Nitrogen Donor Ligands ◽  
Nitrogen Donor

DFT studies are carried out on some ligand substitution reactions of tetramethylcuprate(III) (TMC) complex with five different nitrogen donor ligands as probe ligands. The geometry optimization of the possible nine model systems and the frequency calculations are carried out at DFT level using LANL2DZ basis set. The selected structural parameters of optimized model systems of Cu(III) complexes are reported and discussed. The change in the M-C bond distance in TMC due to substitution by probe ligands is explained. Natural population analysis (NPA) has been carried out for these complexes to establish the charge of copper in these complexes. A detailed population analysis of valence orbitals of copper complexes supports the existence of d8 configuration for metal in complexes and there is evidence for the transmission of electrons from the nitrogen donor atom to dxy, dx2-y2, and 4s orbitals. Bond order calculations have been performed for all the complexes to probe the interaction between Cu(III) and the ligand. The stability of the complexes is ascertained from the computed chemical hardness. In order to understand the nature of Cu(III)-L (L = N donors) and Cu(III)-Me bonds in different complexes, Energy Decomposition Analysis (EDA) has been carried out for all the complexes chosen in the theoretical study. Thermodynamic feasibility of these reactions is investigated in terms of free energy changes of these reactions.

The Affinity of Indium(III) for Nitrogen-donor Ligands in Aqueous Solution. A Study of the Complexing of Indium(III) with Polyamines by Differential Pulse Voltammetry, Density Functional Theory, and Crystallography

2007 ◽  
Vol 62 (3) ◽  
pp. 386-396 ◽  
Author(s):  
James M Harrington ◽  
Karen A. Oscarson ◽  
S. Bart Jones ◽  
Joseph H. Reibenspies ◽  
Libero J. Bartolotti ◽  
...  
Keyword(s):  
Dft Calculations ◽  
Differential Pulse Voltammetry ◽  
Density Functional ◽  
Differential Pulse ◽  
Formation Constants ◽  
Donor Ligands ◽  
Nitrogen Donor Ligands ◽  
Diglycolic Acid ◽  
Nitrogen Donor ◽  
Pulse Voltammetry

The affinity of In(III) for N-donor ligands was investigated by differential pulse voltammetry, DFT calculations, and crystallography. The structure of [In(tpen)(CH3COO)](ClO4)2 ・ 0.5H2O (1) is reported (tpen = N,N,N´ ,N´-tetrakis(2-pyridylmethyl)ethylenediamine): Monoclinic, P21/n, a = 8.687(4), b = 7.767(8), c = 20.432(10) Å , β = 93.372(8)°, Z = 4, R = 0.0518. The In(III) center is 7-coordinate, with six In-N bonds to the tpen ligand in the range 2.306 - 2.410 Å, and a unidentate acetate group with In-O = 2.247 Å. The formation constants of In3+ in 0.1 M NaNO3+ at 25 °C are (M = In(III), L = ligand, H = proton): L = triethylenetetramine, logβ (MLH2) = 25.3±}0.3, logK1 = 14.43±}0.09, and logβ (ML(OH)2) = 27.7±}0.1; tetraethylenepentamine, logβ (MLH) = 20.8±}0.2, and ML (logβ (ML) = 20.1±}0.3); diglycolic acid, (logβ (MLH) = 8.06±}0.06), logK1 = 6.02±} 0.06, logβ2 = 9.40±}0.08; tpen, logK1 = 17.71±}0.07; N,N´-bis(2-pyridylmethyl)ethylenediamine, logK1 = 14.69±}0.05; 1,10-phenanthroline, logK1 = 6.81±}0.07, logK2 = 6.44±}0.07, logK3 = 6.20±}0.08. Correlations are shown between the determined formation constants for the polyamines and logK1(NH3) values for a wide variety of metal ions. For M(II) ions, the log K1(NH3) values are experimental data, but for M(III) ions the data are predicted by an empirical dual-basicity equation, including logK1(NH3) = 4.0 for In(III). DFT calculations are used to obtain ΔE for the reaction [M(H2O)6]n+ + NH3 ⇆[M(H2O)5NH3]n+ + H2O for M(II) through M(IV) ions in water, represented as a structureless medium with the dielectric constant of water. Correlations are found that support the predicted value of logK1(NH3) for In(III) of 4.0. The nature of the intercepts on such correlations are discussed.

A DFT investigation of axial N-donor ligands effects on the high valent manganese-oxo meso-tetraphenyl porphyrin

2015 ◽  
Vol 19 (05) ◽  
pp. 651-662 ◽  
Author(s):  
Hossein Kavousi ◽  
Abdolreza Rezaeifard ◽  
Heidar Raissi ◽  
Maasoumeh Jafarpour
Keyword(s):  
Density Functional ◽  
Chemical Potential ◽  
Water Solution ◽  
Nbo Analysis ◽  
Basis Set ◽  
Donor Ligands ◽  
Chemical Hardness ◽  
B3lyp Method ◽  
Nitrogen Donors ◽  
High Valent

The effect of different electronic and structural nitrogen donors (L) on the N ( ax )- Mn - O properties in the high valent manganese-oxo meso-tetraphenylporphyrin intermediate is investigated by the density functional B3LYP method with 6-31g* basis set. The geometric structures, frontier molecular orbitals, thermodynamic parameters and physical properties such as chemical potential and chemical hardness of [( TPP )( L ) MnO ]+ complexes in the gas phase as well as water solution are calculated. Our theoretical results confirm that the Mn - O distances in [( TPP )( L ) MnO ]+ species decrease by replacing imidazoles with pyridines, amins as well as electron-poor and hindered nitrogen donors resulting from extending the Mn – N ( ax ) bonds. These results are supported by vibrational frequencies, atoms in molecules (AIM) and natural bond orbital (NBO) analysis. It is worth mentioning that the co-catalytic activity trend of different nitrogen donors observed experimentally in the presence of title Mn porphyrin is consistent with the calculated Mn – N ( ax ) and Mn – O bond lengths in this work.

2,4-Dimorpholino-4-yl-6-(4-nitrophenoxy)-[1,3,5]-triazine: Structural and spectroscopic study using experimental and DFT method

2020 ◽  
Vol 0 (0) ◽  
Author(s):  
R. Kavipriya ◽  
Helen P. Kavitha ◽  
B. Karthikeyan ◽  
Jasmine P. Vennila ◽  
Lydia Rhyman ◽  
...  
Keyword(s):  
Density Functional ◽  
Chemical Potential ◽  
Structural Parameters ◽  
Dft Method ◽  
Vibrational Frequencies ◽  
Basis Set ◽  
Chemical Hardness ◽  
Charge Delocalization ◽  
The Fourier Transform ◽  
Molecular Orbital Analysis

Abstract2,4-Dimorpholino-4-yl-6-(4-nitrophenoxy)-[1,3,5]-triazine (DMNT) was synthesized and the molecular structure and vibrational frequencies were studied by density functional theory (DFT) method. The functional used was Becke’s three parameter exchange functional combined with the Lee-Yang-Parr correlation (B3LYP) and the standard basis set was 6-31G(d) for all atoms. The Fourier Transform-Infra Red (FT-IR) and FT-Raman spectra of DMNT were recorded and complete assignments of the observed vibrational frequencies are done. The assignments were confirmed by isotopic labelling. The structural parameters, harmonic vibrational frequencies, IR intensities and Raman intensities of DMNT in the ground-state were also computed. Non-linear optical behaviour of DMNT was analysed by examining the properties like electric dipole moment, polarizability and hyperpolarizability. Molecular properties such as ionization potential, electro-negativity, chemical potential and chemical hardness were obtained from molecular orbital analysis. Hyper conjugative interaction and charge delocalization taking place in DMNT was confirmed by Natural bond analysis studies. UV-Vis spectrum of DMNT was also recorded to understand the electronic properties.Graphical Abstract:

Quantum Mechanical Investigation of Geometrical Structure and Dynamic Behavior of h-BNNT (9,9-5) and h-AlNNT (9,9-5)Single-Walled Nanotubes: NBO Analysis

2019 ◽  
Vol 16 (9) ◽  
pp. 705-717
Author(s):  
Mehrnoosh Khaleghian ◽  
Fatemeh Azarakhshi
Keyword(s):  
Carbon Nanotubes ◽  
Density Functional ◽  
Structural Parameters ◽  
Energy Levels ◽  
Nbo Analysis ◽  
Electronic Energy ◽  
Boron Nitride Nanotubes ◽  
Basis Set ◽  
B3lyp Method ◽  
Mechanical Investigation

In the present research, B45H36N45 Born Nitride (9,9) nanotube (BNNT) and Al45H36N45 Aluminum nitride (9,9) nanotube (AlNNT) have been studied, both having the same length of 5 angstroms. The main reason for choosing boron nitride nanotubes is their interesting properties compared with carbon nanotubes. For example, resistance to oxidation at high temperatures, chemical and thermal stability higher rather than carbon nanotubes and conductivity in these nanotubes, unlike carbon nanotubes, does not depend on the type of nanotube chirality. The method used in this study is the density functional theory (DFT) at Becke3, Lee-Yang-Parr (B3LYP) method and 6-31G* basis set for all the calculations. At first, the samples were simulated and then the optimized structure was obtained using Gaussian 09 software. The structural parameters of each nanotube were determined in 5 layers. Frequency calculations in order to extract the thermodynamic parameters and natural bond orbital (NBO) calculations have been performed to evaluate the electron density and electrostatic environment of different layers, energy levels and related parameters, such as ionization energy and electronic energy, bond gap energy and the share of hybrid orbitals of different layers.

scholarly journals Exo⇔Endo Isomerism, MEP/DFT, XRD/HSA-Interactions of 2,5-Dimethoxybenzaldehyde: Thermal, 1BNA-Docking, Optical, and TD-DFT Studies

Molecules ◽  
2020 ◽  
Vol 25 (24) ◽  
pp. 5970
Author(s):  
Nabil Al-Zaqri ◽  
Mohammed Suleiman ◽  
Anas Al-Ali ◽  
Khaled Alkanad ◽  
Karthik Kumara ◽  
...  
Keyword(s):  
Density Functional ◽  
Energy Gap ◽  
Structural Parameters ◽  
Population Analysis ◽  
Xrd Analysis ◽  
X Ray Diffraction ◽  
Optical Energy Gap ◽  
Functional Theory ◽  
Reactivity Descriptors ◽  
Td Dft

The exo⇔endo isomerization of 2,5-dimethoxybenzaldehyde was theoretically studied by density functional theory (DFT) to examine its favored conformers via sp2–sp2 single rotation. Both isomers were docked against 1BNA DNA to elucidate their binding ability, and the DFT-computed structural parameters results were matched with the X-ray diffraction (XRD) crystallographic parameters. XRD analysis showed that the exo-isomer was structurally favored and was also considered as the kinetically preferred isomer, while several hydrogen-bonding interactions detected in the crystal lattice by XRD were in good agreement with the Hirshfeld surface analysis calculations. The molecular electrostatic potential, Mulliken and natural population analysis charges, frontier molecular orbitals (HOMO/LUMO), and global reactivity descriptors quantum parameters were also determined at the B3LYP/6-311G(d,p) level of theory. The computed electronic calculations, i.e., TD-SCF/DFT, B3LYP-IR, NMR-DB, and GIAO-NMR, were compared to the experimental UV–Vis., optical energy gap, FTIR, and 1H-NMR, respectively. The thermal behavior of 2,5-dimethoxybenzaldehyde was also evaluated in an open atmosphere by a thermogravimetric–derivative thermogravimetric analysis, indicating its stability up to 95 °C.

The role of zero-field splitting and π-stacking interaction of different nitrogen-donor ligands on the optical properties of luminescent rhenium tricarbonyl complexes

2021 ◽  
Author(s):  
Plinio Cantero-López ◽  
Yoan Hidalgo-Rosa ◽  
Zoraida Sandoval-Olivares ◽  
Julián Santoyo-Flores ◽  
Pablo Mella ◽  
...  
Keyword(s):  
Excited States ◽  
Coordination Compounds ◽  
Donor Ligands ◽  
Zero Field ◽  
Zero Field Splitting ◽  
Nitrogen Donor Ligands ◽  
Nitrogen Donor ◽  
Π Stacking Interaction ◽  
Rhenium Tricarbonyl

Rhenium tricarbonyl complexes are one of the most important classes of coordination compounds in inorganic chemistry. Exploring their luminescent excited states, lowest singlet (S1), and the lowest triplet (T1), is...

scholarly journals New Synthetic Routes Toward Enantiopure Nitrogen Donor Ligands.

ChemInform ◽  
2007 ◽  
Vol 38 (15) ◽  
Author(s):  
Xavier Sala ◽  
Anna M. Rodriguez ◽  
Montserrat Rodriguez ◽  
Isabel Romero ◽  
Teodor Parella ◽  
...  
Keyword(s):  
Donor Ligands ◽  
Nitrogen Donor Ligands ◽  
Nitrogen Donor ◽  
Synthetic Routes

Oxidative Degradation of Toxic Organic Pollutants by Water Soluble Nonheme Iron(IV)-Oxo Complexes of Polydentate Nitrogen Donor Ligands

2021 ◽  
Author(s):  
Sandip Munshi ◽  
Rahul Dev Jana ◽  
Tapan Kanti Paine
Keyword(s):  
Organic Pollutants ◽  
Oxidative Degradation ◽  
Heme Iron ◽  
Water Soluble ◽  
Donor Ligands ◽  
Nitrogen Donor Ligands ◽  
Polydentate Ligands ◽  
Oxo Complexes ◽  
Non Heme Iron ◽  
Nitrogen Donor

The ability of four mononuclear non-heme iron(IV)-oxo complexes supported by nitrogen donor polydentate ligands in degrading organic pollutants has been investigated. The water soluble iron(II) complexes upon treatment with ceric...

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