A 3D-RISM-SCF method with dual solvent boxes for a highly polarized system: application to 1,6-anhydrosugar formation reaction of phenyl α- and β-d-glucosides under basic conditions

Aono, Shinji; Hosoya, Takashi; Sakaki, Shigeyoshi

doi:10.1039/c3cp43892a

Cited by 12 publications

(17 citation statements)

References 66 publications

(75 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…For making comparison of absorption and emission spectra between crystal and solution phases, we performed the three-region 3D-RISM-SCF-DFT calculation with the B3LYP-D3 functional to determine the geometry of solute and solvation structure of CHCl 3 , because the absorption spectrum was experimentally observed in CHCl 3 . The optimization threshold of energy gradient was taken to be the same as that (0.0008 au b –1 ) in the QM/MM calculation for the crystal phase.…”

Section: Computational Detailsmentioning

confidence: 99%

Dependence of Absorption and Emission Spectra on Polymorphs of Gold(I) Isocyanide Complexes: Theoretical Study with QM/MM Approach

et al. 2019

Self Cite

View full text Add to dashboard Cite

We theoretically investigated phenyl(phenyl isocyanide) gold(I) (PhNC)Au(Ph) 1 and phenyl(dimethylphenyl isocyanide) gold(I) (dimPhNC)Au(Ph) 2 in crystal using our periodic quantum mechanics/molecular mechanics (QM/MM) method based on the self-consistent point charges to elucidate interesting mechano-chemical changes of absorption and emission spectra of 1 and 2 in crystal. To characterize 1 and 2 in crystal, their absorption and emission spectra in crystal were compared to those in gas phase and CHCl3 solvent, where a three-dimensional reference interaction site model self-consistent field (3D-RISM-SCF) was employed to incorporate solvation effect. To investigate the phosphorescence spectrum in crystal, we optimized the geometry of the molecule at the triplet state in crystal which had ground-state geometry because the population of the excited state is generally very small. The QM/MM calculations showed that 1 formed two polymorphs 1b and 1y, 2 formed two polymorphs 2b and 2g, and 1y was more stable than 1b, which agree with the experimental findings. In 1b and 2b, the ligand-to-ligand charge transfer state is the lowest-energy excited state in the absorption, and the π–π* locally excited state on the PhNC moiety is the lowest-energy triplet state in the emission. In 1y and 2g, on the other hand, the metal–metal-to-ligand charge transfer (MMLCT) state is the lowest-energy excited state in both absorption and emission. These characteristic differences between two crystal structures arise from the geometrical features that the Au–Au distance is much shorter in 1y and 2g than in 1b and 1y and the intermolecular torsion angle η between two Au-PhNC moieties is much smaller in 1y and 2g than in 1b and 2b, respectively; the short Au–Au distance raises the energy level of antibonding orbital consisting of two Au dσ orbitals, and the small η angle lowers the energy level of bonding orbital consisting of two PhNC π* orbitals, leading to the presence of a lower-energy MMLCT state. The QM/MM calculations also disclosed intramolecular torsion angle τ between the Ph and PhNC planes and CH−π interaction of the Ph plane significantly influence absorption spectrum. Based on those computational results, discussion is presented on the differences in absorption and emission spectra among gas, solution, and crystal, the assignments of experimentally observed excitation and emission spectra in crystal, and their energy shifts induced by single-crystal-to-single-crystal phase transition.

show abstract

Section: Computational Detailsmentioning

confidence: 99%

Dependence of Absorption and Emission Spectra on Polymorphs of Gold(I) Isocyanide Complexes: Theoretical Study with QM/MM Approach

et al. 2019

Self Cite

View full text Add to dashboard Cite

show abstract

“…This 3D-RISM-SCF method was successfully applied to hydrolysis of cis-platin 134 and 1,6-anhydrosugar formation of phenyl α-and β-D-glucosides under basic conditions. 135 Mixed-valence compounds are one of the most important systems in which solvation plays crucial roles. 136 As is well known, mixed-valence systems are classified into three categories, according to Robin and Day; 137 in Class-I, the system has two electronic structures but one electronic structure is 139 Apparently, the solvation effect is very important in mixed-valence systems, because the localized electronic structure is stabilized very much by polar solvent but the delocalized structure is influenced little by solvent.…”

Section: Solvation Effectsmentioning

confidence: 99%

Theoretical and Computational Study of a Complex System Consisting of Transition Metal Element(s): How to Understand and Predict Its Geometry, Bonding Nature, Molecular Property, and Reaction Behavior

Sakaki

2015

Bulletin of the Chemical Society of Japan

Self Cite

View full text Add to dashboard Cite

Complex chemical systems consisting of transition metal element(s) are important and attractive research targets in both experimental chemistry and theoretical chemistry. Transition-metal complexes with carbon dioxide are discussed as one example, in which the coordination geometry, bonding nature, and reactivity are understood well and predicted with the HOMO and the number of d electrons. The spin-multiplicity of inverse sandwich-type dinuclear transition-metal complexes, which have been synthesized recently as a new type of compound, is discussed as another example based on CASPT2 calculations, in which the clear relationship between the spin multiplicity of its ground state and the number of d electrons is presented. Theoretical understanding of various organometallic reactions has been an important endeavor over the last two decades. Insertion reactions of olefin and carbon dioxide into MH and Malkyl bonds and σ-bond activation reactions are discussed with orbital interaction diagrams based on perturbation theory. In particular, detailed discussion of the characteristic features of a new type of oxidative addition to an ML moiety (L = neutral ligand such as alkene and alkyne) and heterolytic σ-bond activation by an MX moiety (X = anionic ligand). It is still a central challenge to elucidate the reaction mechanisms of catalytic reactions by transition metal complexes. The reaction mechanisms and electronic processes of Ru-catalyzed hydrogenation of carbon dioxide, Pt-, Rh-, and Zr-catalyzed hydrosilylations of alkene, Ir-catalyzed borylation of benzene, and the Hiyama cross-coupling reaction are analyzed based on computational results. We wish to present how to understand the mechanism based on the number of d electrons and the energy of d orbitals in discussion. Also, the importance of solvation and crystalline effects in the theoretical study of transition-metal complexes is discussed based on our recent theoretical studies of mixed-valence complex and a single crystal of a Pt(II) complex.

show abstract

“…The existence of unprotected 1,2-anhydro sugars has been rationalized by a theoretical study for levoglucosan formation from phenyl β-glucoside. [64] Bennet and co-workers reported that the hydrolysis of p-nitrophenyl glycosides proceeds through a mechanism involving formation of 1,2-anhydro sugar intermediates. [65] However, the direct experimental observation of unprotected 1,2-anhydro sugars had not been achieved in spite of their potential utilities in organic synthesis.…”

Section: First Detection Of Unprotected 12-anhydro Sugarsmentioning

confidence: 99%

Chemistry of 1,2-Anhydro Sugars

Noguchi

Serizawa

et al. 2018

Chimia

View full text Add to dashboard Cite

The 1,2-anhydro sugars are a class of valuable and versatile intermediates in carbohydrate chemistry. In the first part of this article, a review is given on preparation methods of 1,2-anhydro sugars that are suitably protected. Protected 1,2-anhydro sugars have been widely used as glycosyl donors for the synthesis of glycosyl compounds such as oligosaccharides and nucleosides. In the second part, a brief history and the chemistry of unprotected 1,2-anhydro sugars is described. In the past few years, our research group has developed protection-free methods for synthesis of glycosyl compounds through unprotected 1,2-anhydro sugars as reactive intermediates based on the concept of 'direct anomeric activation'. In this article, the one-step preparation of glycosyl compounds such as thioglycoside derivatives and glycosyl azides by using formamidinium-type dehydrating agents is presented. Furthermore, the initial results on the first detection of unprotected 1,2-anhydro sugar intermediates by NMR measurements are shown along with their full structure characterizations.

show abstract

A 3D-RISM-SCF method with dual solvent boxes for a highly polarized system: application to 1,6-anhydrosugar formation reaction of phenyl α- and β-d-glucosides under basic conditions

Cited by 12 publications

References 66 publications

Dependence of Absorption and Emission Spectra on Polymorphs of Gold(I) Isocyanide Complexes: Theoretical Study with QM/MM Approach

Dependence of Absorption and Emission Spectra on Polymorphs of Gold(I) Isocyanide Complexes: Theoretical Study with QM/MM Approach

Theoretical and Computational Study of a Complex System Consisting of Transition Metal Element(s): How to Understand and Predict Its Geometry, Bonding Nature, Molecular Property, and Reaction Behavior

Chemistry of 1,2-Anhydro Sugars

Contact Info

Product

Resources

About