Update 2 of: Electrophilicity Index

An experimental and theoretical study of the hetero Diels–Alder reactions between (E)-2-aryl-1-cyano-1-nitroethenes and ethyl vinyl ether: one-step or zwitterionic, two-step mechanism?

“…To investigate reactions between (E)-2-aryl-1-cyano-1-nitroethenes 1a-f and ethyl vinyl ether 2 before beginning experimental study, we analyzed the electronic interactions of addents using the theory of DFT reactivity indices [13,14,32] ( Table 4). Indices of global electrophilicity (x) [33], global nucleophilicity (N) [34] as well as local descriptors x k , N k required for this purpose were calculated by using the Parr functions [32] and the equations recommended by Domingo et al [13,15].…”

“…In this work, we decided to resolve this problem on the basis of an experimental kinetic study as well as quantum chemical considerations. In particular, we performed: (i) analysis of the nature of addends interactions with respect to the recently strongly developed [12][13][14][15] application of the reactivity indices defined within the conceptual DFT, (ii) study about kinetic substituent effects, (iii) study about kinetic solvent effects, (iv) quantum chemical simulations of reaction paths. In our study, we used a series of (E)-2-aryl-1-cyano-1-nitroethenes nitroalkenes (1a-f) containing substituents with different electronic properties (Scheme 2).…”

Molecular dynamics and density functional theory study on the corrosion inhibition of austenitic stainless steel in hydrochloric acid by two pyrimidine compounds

“…These calculations were performed to investigate the structural parameters that affect the inhibition efficiency of the two pyrimidine derivatives and also to study the adsorption mechanisms on the austenitic stainless steel surface. From the optimized geometries of BCPTI and BTPTT, their global molecular descriptors [31][32][33][34][35][36][37][38][39][40][41][42][43][44] such as the energy of the highest occupied molecular orbital (E HOMO ), the energy of the lowest unoccupied molecular orbital (E LUMO ), the energy gap (DE), the ionization potential (IP), the electron affinity (EA), the global hardness (g), the electronegativity (v), the global softness (r), the electrophilicity (x), the electrodonating (x -), the electroaccepting (x ? ), the net electrophilicity (Dx ± ), the fraction of electron transferred (DN), the total negative charge (TNC) and the dipole moment (l) were calculated.…”

An experimental and quantumchemical study of [2+3] cycloaddition between (Z)-C-(m,m,p-trimethoxyphenyl)-N-(p-methyphenyl)-nitrone and (E)-3,3,3-trichloro-1-nitroprop-1-ene: mechanistic aspects

“…In particular, we decided: (i) to analyse the nature of addent interactions with respect to the theory, developed intensively in recent years [14][15][16][17][18] , of electrophilicity and nucleophilicity indexes, (ii) identify reaction stereochemistry, (iii) perform kinetic studies (determination of activation parameters and the kinetic solvent effect), and (iv) perform quantumchemical simulations of actual reaction pathways. Such a comprehensive approach should in our opinion give a clear view of the course of the reaction in question and make a large contribution to our knowledge of the mechanistic aspects of nitrone [2+3] cycloaddition.…”