In this work, the theoretical description of the 4- and 3-substituted-cinnamic acid esterification with different electron donating and electron withdrawing groups was performed at the B3LYP and M06-2X levels, as a two-step process: the O-protonation and the nucleophile attack by ethanol. In parallel, an experimental work devoted to the synthesis and characterization of the substituted-cinnamat...

Chemistry of the actinide elements represents a challenging yet vital scientific frontier. Development of actinide chemistry requires fundamental understanding of the relative roles of actinide valence-region orbitals and the nature of their chemical bonding. We report here an experimental and theoretical investigation of the uranium methylidyne molecules X3U'CH (X F, Cl, Br), F2ClU'CH, and F3U...

Open-shell fragments of graphene have attracted increased attention in recent years because oftheir unique spin carrier property. Through the experimental efforts, these neutral π-radicals could bestabilized by steric protection or delocalized π-conjugated system, such as the phenalenyl-basedmolecules. Here, we use zero sum rule to extend the molecular size and investigate their...

where Xis called the nucleophile, RjR2R3ZY the substrate and Ythe leaving group. The substrate structure, the nature of the nucleophile, of the reaction center Z and of the leaving group, and the nature of the solvent are important factors of the overall rate of reaction. Now, experimentsare available for studying solvated ions in the gas-phase, it is possible to explore the transition state in...

Based on the relationship between average local ionization energy Ī(r) and electron affinity Ā(r) with electronic Fukui functions, i.e., f−(r) f+(r), respectively, in this paper, we establish a connection nuclear functions beyond frontier molecular orbitals. As consequence of connection, obtain expressions interpreted as variation nucleophilicity or electrophilicity (weighted by orbital functio...

In this study, we theoretically investigated Methyl hydrazinecarbodithioate by quantum chemical calculations for geometry optimization, vibration frequencies, and electronic structure parameters. The geometry optimization by DFT, ab initio MP2 method and the frequency calculation by DFT method was performed at the highest available Pople style 6-311G++(3df,3pd) basis set level. The semi-emp...

The class of compounds (RCp)2MX2, where M is a group IV metal, Cp is cyclopentadienyl, R is an alkyl, and X is a halide, has been of continuing interest as precursors for olefin coordination polymerization catalysts. In this communication, we demonstrate that the technique of optically detected magnetic resonance (ODMR) reveals subtle differences in the composition of the frontier molecular orb...

Density functional theory investigations indicate that carbon boronyls (CBO)n (n = 3-7) are considerably more stable in thermodynamics than their boron carbonyl isomers (BCO)n and exhibit aromaticity throughout the whole series. The extra stabilities of (CBO)n originate from their frontier pi molecular orbitals delocalized over the Dnh Cn central rings which are absent in (BCO)n. It is expected...