scholarly journals Mechanistic insights into the insertion and addition reactions of group 13 analogues of the six-membered N-heterocyclic carbenes: interplay of electrophilicity, basicity, and aromaticity governing the reactivity

RSC Advances ◽  
2021 ◽  
Vol 11 (33) ◽  
pp. 20070-20080
Author(s):  
Zheng-Feng Zhang ◽  
Ming-Der Su
Keyword(s):  
Theoretical Study ◽  
Chemical Reactivity ◽  
Atomic Radius ◽  
Theoretical Models ◽  
Membered Ring ◽  
Heterocyclic Carbenes ◽  
Addition Reactions ◽  
Group 13

On the basis of sophisticated theoretical models, the theoretical study demonstrated that the atomic radius of a group 13 element in a six-membered-ring NHC analogue plays an important role in determining its chemical reactivity.

Recent advances in synthesis of organometallic complexes of indium

2020 ◽  
Vol 40 (3) ◽  
pp. 107-151
Author(s):  
Hira Anwar ◽  
Rosenani A. Haque ◽  
Rahman Shah Zaib Saleem ◽  
Muhammad Adnan Iqbal
Keyword(s):  
Material Science ◽  
Thin Film Transistors ◽  
Heterocyclic Carbenes ◽  
Organometallic Complexes ◽  
Organic Ligands ◽  
Group 13 ◽  
Indium Complexes ◽  
Different Types ◽  
Stirring Time ◽  
Different Temperatures

AbstractThe indium complexes are being used in many applications like catalysis, optoelectronics, sensors, solar cells, biochemistry, medicine, infrared (IR) mirrors and thin-film transistors (TFTs). In organometallic complexes of indium, it forms different types of complexes with single, double, triple and tetra linkages by coordinating with numerous elements like C, N, O and S and also with some other elements like Se and Ru. So, the present study comprises all the possible ways to synthesize the indium complexes by reacting with different organic ligands; most of them are N-heterocyclic carbenes, amines, amides and phenols. The commonly used solvents for these syntheses are tetrahydrofuran, dichloromethane, toluene, benzene, dimethyl sulfoxide (DMSO) and water. According to the nature of the ligands, indium complexes were reported at different temperatures and stirring time. Because of their unique characteristics, the organometallic chemistry of group 13 metal indium complexes remains a subject of continuing interest in synthetic chemistry as well as material science.

scholarly journals Theoretical Study of Zirconium Isomorphous Substitution into Zeolite Frameworks

Molecules ◽  
2019 ◽  
Vol 24 (24) ◽  
pp. 4466
Author(s):  
Duichun Li ◽  
Bin Xing ◽  
Baojun Wang ◽  
Ruifeng Li
Keyword(s):  
Acid Site ◽  
Density Functional ◽  
Theoretical Study ◽  
Atomic Radius ◽  
Acid Sites ◽  
Isomorphous Substitution ◽  
Dispersion Correction ◽  
Brønsted Acidity ◽  
Functional Theory ◽  
Brönsted Acidity

Systematic periodic density functional theory computations including dispersion correction (DFT-D) were carried out to determine the preferred location site of Zr atoms in sodalite (SOD) and CHA-type topology frameworks, including alumino-phosphate-34 (AlPO-34) and silico-alumino-phosphate-34 (SAPO-34), and to determine the relative stability and Brönsted acidity of Zr-substituted forms of SOD, AlPO-34, and SAPO-34. Mono and multiple Zr atom substitutions were considered. The Zr substitution causes obvious structural distortion because of the larger atomic radius of Zr than that of Si, however, Zr-substituted forms of zeolites are found to be more stable than pristine zeolites. Our results demonstrate that in the most stable configurations, the preferred favorable substitutions of Zr in substituted SOD have Zr located at the neighboring sites of the Al-substituted site. However, in the AlPO-34 and SAPO-34 frameworks, the Zr atoms are more easily distributed in a dispersed form, rather than being centralized. Brönsted acidity of substituted zeolites strongly depends on Zr content. For SOD, substitution of Zr atoms reduces Brönsted acidity. However, for Zr-substituted forms of AlPO-34 and SAPO-34, Brönsted acidity of the Zr-O(H)-Al acid sites are, at first, reduced and, then, the presence of Zr atoms substantially increased Brönsted acidity of the Zr-O(H)-Al acid site. The results in the SAPO-34-Zr indicate that more Zr atoms substantially increase Brönsted acidity of the Si-O(H)-Al acid site. It is suggested that substituted heteroatoms play an important role in regulating and controlling structural stability and Brönsted acidity of zeolites.

Theoretical Study of Addition Reactions of SiX2to Acetylene (X = H, CH3, t-Bu, Cl, F)

1999 ◽  
Vol 18 (23) ◽  
pp. 4881-4883 ◽  
Author(s):  
Gyusung Chung ◽  
Mark S. Gordon
Keyword(s):  
Theoretical Study ◽  
Addition Reactions

Study of the Stability and Chemical Reactivity of a Series of Tetrazole Pyrimidine Hybrids by the Density Functional Theory Method (DFT)

2021 ◽  
Vol 37 (4) ◽  
pp. 805-812
Author(s):  
Ahissandonatien Ehouman ◽  
Adjoumanirodrigue Kouakou ◽  
Fatogoma Diarrassouba ◽  
Hakim Abdel Aziz Ouattara ◽  
Paulin Marius Niamien
Keyword(s):  
Density Functional ◽  
Theoretical Study ◽  
Molecular Descriptors ◽  
Chemical Reactivity ◽  
Density Functional Theory Method ◽  
Functional Theory ◽  
Reactivity Descriptors ◽  
The Density Functional Theory ◽  
The Stability ◽  
Global Reactivity Descriptors

Our theoretical study of stability and reactivity was carried out on six (06) molecules of a series of pyrimidine tetrazole hybrids (PTH) substituted with H, F, Cl, Br, OCH3 and CH3 atoms and groups of atoms using the density function theory (DFT). Analysis of the thermodynamic formation quantities confirmed the formation and existence of the series of molecules studied. Quantum chemical calculations at the B3LYP / 6-311G (d, p) level of theory determined molecular descriptors. Global reactivity descriptors were also determined and analyzed. Thus, the results showed that the compound PTH_1 is the most stable, and PTH_5 is the most reactive and nucleophilic. Similarly, the compound PTH_4 is the most electrophilic. The analysis of the local descriptors and the boundary molecular orbitals allowed us to identify the preferred atoms for electrophilic and nucleophilic attacks.

Theoretical study of the mechanism for the sequential N–O and N–N bond cleavage within N2O adducts of N-heterocyclic carbenes by a vanadium(iii) complex

2016 ◽  
Vol 45 (3) ◽  
pp. 1047-1054 ◽  
Author(s):  
Robert Robinson ◽  
Miranda F. Shaw ◽  
Robert Stranger ◽  
Brian F. Yates
Keyword(s):  
Theoretical Study ◽  
Bond Cleavage ◽  
Heterocyclic Carbenes

The addition of N-heterocyclic carbene (NHC) increases the activity of N2O towards cleavage of both the N–O and N–N bonds.

scholarly journals Theoretical Study of the Reaction of Formation of Some Free Phosphines by Stereoselective Hydrophosphination through DFT Method

2018 ◽  
pp. 1-10
Author(s):  
Kouadio Valery Bohoussou ◽  
Anoubilé Bénié ◽  
Mamadou Guy-Richard Koné ◽  
N’guessan Yao Silvère Diki ◽  
Kafoumba Bamba ◽  
...  
Keyword(s):  
Theoretical Study ◽  
Chemical Reactivity ◽  
Dft Method ◽  
Trans Form ◽  
Dft Methods ◽  
Activation Barriers ◽  
Reactivity Descriptors ◽  
Chemical Reactivity Descriptors ◽  
Theoretical Results ◽  
Cis Isomer

In this work the formation of vinylphosphines was studied through the hydrophosphination reaction. The study aims to rationalize the stereoselectivity of these compounds using quantum DFT methods. This theoretical study of chemical reactivity was conducted at B3LYP/6-311 + G (d, p) level. Global chemical reactivity descriptors, stationary point energies and activation barriers were examined to foretell the relative stability of the stereoisomers formed. The various results obtained have revealed that the addition of arylphosphine to dihalogenoacetylene is stereospecific. The Trans form of vinylphosphines is more stable than the Cis form, when the substituent on phosphorus generates less or no π-conjugations. On the other hand, the Cis isomer is predominant when the aryl radical favors more π-conjugations. The theoretical results obtained are in agreement with the experimental results.

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