Chuan-Feng Wang

CARBON DIOXIDE ACTIVATION BY Y ATOM AND Y+ CATION IN THE GAS PHASE: A DENSITY FUNCTIONAL THEORETICAL STUDY

ABSTRACT The potential energy surfaces for the Y+CO 2 and Y + +CO 2 reactions have been investigated by using the DFT (B3LYP/ECP/6−311+G*) level of theory. Both ground and excited state potential energy surfaces are discussed. The present results show that the reaction mechanism is an insertion mechanism along the C−O bond activation branch. The reaction of Y atom with CO 2 was shown to occur preferentially on the doublet PES throughout the reaction process. As for the reaction between Y + cation with CO 2 , it involves potential energy curve-crossing which dramatically affects reaction mechanism. Due to the intersystem crossing existing in the reaction process of Y + with CO 2 , the intermediate (OY(η 2 CO)) + may not form. This mechanism is different from that of Y + CO 2 system. All our theoretical results not only support the existing conclusions inferred from early experiment, but also complement the pathway and mechanism for this reaction. Keywords: DFT theory, Potential energy surface, Intersystem, Yttrium

A novel azide copper complex: [[Azido{bis[2-(piperidin-1-ylmethyl)pyridine]}copper(II)]perchlorate] hydrate

Synthesis and single crystal X-ray diffraction study were carried for compound {[Cu(C11H16N4)2(N3)](ClO4)} · H2O (I). The structure is molecular, and the Cu2+ ion is in a five-coordinated compressed trigonal bipyramid environment. Copper ion is bound to five N atoms, in which four N atoms are from two chlelating ligands 2-(piperidin-1-ylmethyl)pyridine and the fifth N donor is from a monodentate azido ligand. The complex cations [Cu(C11H16N4)2(N3)]+, the perchlorate anions, and solvent water molecules are further joined into three dimensional supramolecular networks by rich hydrogen bonds including strong O-H…N between solvent water and azide ion and O-H…O between solvent water and perchlorate ion, and weak hydrogen bonds C-H…O, and weak bifurcated hydrogen bonds C-H/C-H…N in which N atom of azide ion serving as bifurcated acceptor and two C-H groups as donors.

Reaction of CH3CHO with Y+: A density functional theoretical study

The reaction mechanism of the Y+ cation with CH3CHO has been investigated with a DFT approach. All the stationary points are determined at the UB3LYP/ECP/6-311++G** level of the theory. Both ground and excited state potential energy surfaces are investigated in detail. The present results show that the title reaction start with the formation of a CH3CHO-metal complex followed by C-C, aldehyde C-H, methyl C-H and C-O activation. These reactions can lead to four different products (Y+CH4 + CO, Y+CO + CH4, Y+COCH2 + H2 and Y+O + C2H4). The minimum energy reaction path is found to involve the spin inversion in the different reaction steps, this potential energy curve-crossing dramatically affects reaction exothermic. The present results may be helpful in understanding the mechanism of the title reaction and further experimental investigation of the reaction.

Theoretical Investigation of the Reaction of Yttrium Cation with Acetone

Abstract The reaction mechanism of Y+ with CH3COCH3 has been investigated with a DFT method. All the stationary points are determined at the UB3LYP/ECP/6-311++G** level of the theory. Both the ground and the excited state potential energy surfaces are investigated in detail. The present results show that the title reaction starts with the formation of an O-attached complex (IM0) followed by C–O, C–H and C–C activation. The minimum energy reaction path is found to involve the spin inversion in the initial reaction step. The potential energy curve-crossing dramatically affects reaction exothermic. The present results may be helpful in understanding the mechanism of the title reaction and further experimental investigation of the reaction.

Theoretical survey of the reaction between osmium and acetaldehyde

The mechanism of the reaction of osmium atom with acetaldehyde has been investigated with a DFT approach. All the stationary points are determined at the UB3LYP/sdd/6-311++G** level of the theory. Both ground and excited state potential energy surfaces are investigated in detail. The present results show that the title reaction start with the formation of a CH3CHO-metal complex followed by C-C, aldehyde C-H, C-O, and methyl C-H activation. These reactions can lead to four different products (HOsCH3 + CO, OsCO + CH4, OsCOCH3 + H, and OsO + C2H4). The minimum energy reaction path is found to involve the spin inversion in the initial reaction step. This potential energy curve-crossing dramatically affects reaction exothermic. The present results may be helpful in understanding the mechanism of the title reaction and further experimental investigation of the reaction.

Gas-phase reactions of pd with acetone: A theoretical investigation using density functional theory

The gas-phase reaction of palladium atom with acetone is investigated using density functional theory. Geometries and energies of the reactants, intermediates, and products involved are calculated. Both ground and excited state potential energy surfaces are investigated in detail. The present results show that the title reaction start with the formation of an η2-CH3COCH3-metal complex, followed by C-O, C-H, and C-C activation. These reactions can lead to four different products (PdO + C3H6, PdCH2COCH3 + H, PdCH2 + CH3CHO, and PdCOCH2 + CH4). The present results may be helpful in understanding the mechanism of the title reaction and further experimental investigation of the reaction.

Supramolecular structure of tetraaquabis[1-(carboxylatomethyl)-1,3-benzimidazol-3-ium-3-acetato-κO] Cadmium(II) dehydrate

A new complex, [Cd(C11H9N2O4)2(H2O)4]·2H2O, was synthesized and studied by X-ray diffraction analysis. The central Cd(II) atom lies on a crystallographic inversion center and is coordinated by four water molecules and two monodentate 1-(carboxymethyl)-1,3-benzimidazol-3-ium-3-acetate ligands in a slightly distorted octahedral geometry. The crystal packing is stabilized by intermolecular O-H…O hydrogen bonds, which generate a three-dimensional framework.

Theoretical investigation of the reactions of La atom and La+ cation with carbonyl sulfide

The potential energy surfaces for the La+SCO and La++ SCO reactions have been theoretically investigated by using the DFT (B3LYP/ECP/6-311+G(2d)) level of theory. Both ground and excited state potential energy surfaces (PES) are discussed. The present results show that the reaction mechanism is insertion mechanism both along the C-S and C-O bond activation branches, but the C-S bond activation is much more favorable in energy than the C-O bond activation. The reaction of La atom with SCO was shown to occur preferentially on the ground state (doublet) PES throughout the reaction process, and the experimentally observed species, have been explained according to the mechanisms revealed in this work. While for the reaction between La+ cation with SCO, it involves potential energy curve-crossing which dramatically affects reaction mechanism, and the crossing points (CPs) have been localized by the approach suggested by Yoshizawa et al. Due to the intersystem crossing existing in the reaction process of La+ with SCO, the products SLa+(η2CO) and OLa+(η2CS) may not form. This mechanism is different from that of La + SCO system. All our theoretical results not only support the existing conclusions inferred from early experiment, but also complement the pathway and mechanism for this reaction.