The parallel π–π stacking: a model study with MP2 and DFT methods

Ye, Xiangyu; Li, Zhenhua; Wang, Wenning; Fan, Kangnian; Xu, Wei; Hua, Zhongyi

doi:10.1016/j.cplett.2004.07.115

Cited by 75 publications

(36 citation statements)

References 26 publications

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“…[46,52] In fact, systematic DFT studies on intermolecular binding of benzene dimer predict weak attractive or repulsive interactions. [45][46] As in previous findings, the interaction energies of benzene dimer and benzene-methane adduct computed at our density functional level are À5.5 and À4.1 kJ mol…”

mentioning

confidence: 88%

Origin of Stereoinduction by Chiral Aminophosphane Phosphinite Ligands in Enantioselective Catalysis: Asymmetric Hydroformylation

Carbó¹,

Lledós²,

Vogt³

et al. 2006

Chemistry A European J

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The origin of stereoinduction by chiral aminophosphane phosphinite (AMPP) ligands in asymmetric hydroformylation was investigated with a theoretical approach. The roles of the stereogenic center at the aminophosphane phosphorus atom (NP*) and of the chirality of the backbone were analyzed by considering three experimentally tested cases: 1) P-stereogenic yielding high ee, 2) P-nonstereogenic yielding low ee, and 3) P-stereogenic yielding low ee. We succeeded in reproducing the experimentally observed trends for the three studied AMPP ligands. Our results indicated that alkene insertion into the rhodium-hydride bond is the selectivity-determining step, and not alkene coordination. Additional calculations on model systems revealed that the different nonbonding weak-type interactions of styrene with the substituents of the NP* stereogenic center in an axial position is responsible for stereodifferentiation. The chirality of the AMPP backbone plays a secondary role. The rationalization of the stereochemical outcome is not straightforward, because two competitive equatorial/axial reaction paths, showing opposite asymmetric induction, must be considered. Construction of stereochemical models and evaluation of stereoinduction for novel ligand systems suggested that two prerequisites are required to improve the performance of AMPP-type ligands in asymmetric hydroformylation: 1) combination of stereorecognition and stereohindrance by substituents at the NP* atom, and 2) more rigid backbones.

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mentioning

confidence: 88%

Origin of Stereoinduction by Chiral Aminophosphane Phosphinite Ligands in Enantioselective Catalysis: Asymmetric Hydroformylation

Carbó¹,

Lledós²,

Vogt³

et al. 2006

Chemistry A European J

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“…26 It has been shown that TDDFT can predict the lowest energy excited states in aromatic aggregates due to the correct description of molecular orbitals. [27][28][29][30] Density functional theory (DFT) cannot completely describe all aspects that contribute to the potential energy surface in π-bound systems, but recently, several studies have predicted reasonable structures for π-π and C-Htπ systems. 31,32 DFT is an attractive choice due to its computational efficiency.…”

Section: Introductionmentioning

confidence: 99%

Theoretical Investigation of Perylene Dimers and Excimers and Their Signatures in X-Ray Diffraction

et al. 2008

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The structures of the ground and excimer states of perylene pairs are calculated [using density functional theory (DFT) and time-dependent DFT techniques] in a free as well as a crystal environment, and their spectroscopic properties are studied for the most stable configurations. The vertical transition energies for the absorption and emission bands are obtained, and they are in good agreement with experimental data. In these calculations, up to six excited states are considered. With the calculated structures of the ground and excimer states, the scattering factors are analyzed as a function of the concentration of excimers in a crystal. The intensity of the 110, 005, and 0 10 0 reflections are found to be fairly sensitive to the presence of excimers in the crystal. The finite (nanosecond) lifetime of the excimer may make it possible to observe this state using time-resolved X-ray diffraction techniques.

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“…Ab initio results have found density functional theory (DFT) to be not completely satisfactory for π -stacking [22][23][24]. Tauer and Sherrill [22] have examined π-π interactions for benzene dimers and trimers and they observed that Møller-Plesset perturbation theory (MP2) used with small basis sets tend to have errors that cancel each other.…”

Section: Discussionmentioning

confidence: 99%

Binding energies for alkane molecules on a carbon surface from gas–solid chromatography and molecular mechanics

Rybolt

Wells

Thomas

et al. 2008

Journal of Colloid and Interface Science

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The parallel π–π stacking: a model study with MP2 and DFT methods

Cited by 75 publications

References 26 publications

Origin of Stereoinduction by Chiral Aminophosphane Phosphinite Ligands in Enantioselective Catalysis: Asymmetric Hydroformylation

Origin of Stereoinduction by Chiral Aminophosphane Phosphinite Ligands in Enantioselective Catalysis: Asymmetric Hydroformylation

Theoretical Investigation of Perylene Dimers and Excimers and Their Signatures in X-Ray Diffraction

Binding energies for alkane molecules on a carbon surface from gas–solid chromatography and molecular mechanics

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