Shigeyoshi Sakaki

Bidirectional Chemo‐Switching of Spin State in a Microporous Framework

The ins and outs of spin: Using the microporous coordination polymer {Fe(pz)[Pt(CN)(4)]} (1, pz=pyrazine), incorporating spin-crossover subunits, two-directional magnetic chemo-switching is achieved at room temperature. In situ magnetic measurements following guest vapor injection show that most guest molecules transform 1 from the low-spin (LS) state to the high-spin (HS) state, whereas CS(2) uniquely causes the reverse HS-to-LS transition.

Self-Accelerating CO Sorption in a Soft Nanoporous Crystal

Soft, Selective CO Sorption Many industrial processes produce CO, which could be used as a chemical feedstock, but separation of CO from other gases, especially N2, is too difficult to be economically viable. Sato et al. (p. 167, published online 12 December 2013) now report that a porous coordination polymer containing Cu2+ ions can selectivity bind CO through serial structural changes reminiscent of allosteric effects in proteins. The separation of CO-N2 mixtures can be achieved with a low input energy for CO desorption. A soft nanoporous crystalline solid exhibits self-accelerating, selective carbon monoxide adsorption. Carbon monoxide (CO) produced in many large-scale industrial oxidation processes is difficult to separate from nitrogen (N2), and afterward, CO is further oxidized to carbon dioxide. Here, we report a soft nanoporous crystalline material that selectively adsorbs CO with adaptable pores, and we present crystallographic evidence that CO molecules can coordinate with copper(II) ions. The unprecedented high selectivity was achieved by the synergetic effect of the local interaction between CO and accessible metal sites and a global transformation of the framework. This transformable crystalline material realized the separation of CO from mixtures with N2, a gas that is the most competitive to CO. The dynamic and efficient molecular trapping and releasing system is reminiscent of sophisticated biological systems such as heme proteins.

Discrete Sandwich Compounds of Monolayer Palladium Sheets

Despite the abundance of “sandwich” complexes, in which two cyclic aromatic hydrocarbon ligands flank a metal center, this motif has not been extended to sheets of multiple metal atoms. We prepared and isolated two such compounds. In the first, three palladium centers form a planar triangular array, capped by chlorides, between two cycloheptatrienyl ligands. In the second, a pentapalladium sheet adopts an edge-sharing triangle-trapezoid skeleton between two naphthacene rings. The compounds were characterized by x-ray crystallography and nuclear magnetic resonance spectroscopy. The nature of bonding in the clusters was analyzed by quantum calculations.

Structures and binding energies of benzene–methane and benzene–benzene complexes. An ab initio SCF/MP2 study

Ab initio SCF/MP2 potentials are calculated on benzene–methane and benzene–benzene complexes. Although no energy stabilization appears at the Hartree–Fock level, a small but non-negligible stabilization in energy is observed at the MP2 level in both complexes, indicating the importance of the dispersion energy. Besides the dispersion energy, the electrostatic interaction plays some role in determining the relative stabilities in several cases. The most stable structure of the benzene–methane complex adopts a C3v symmetry with methane lying on the benzene C6 axis and one hydrogen atom pointing towards benzene. The binding energy of this structure is –1.95 kcal mol–1 from MP2/MIDI-4** calculations and –1.09 kcal mol–1 from MP2/6-31G** calculations, where a p-polarization function is added only on the H atoms of methane. The benzene–methane complex is much less stable than the benzene–benzene complex.

New generation of the reference interaction site model self-consistent field method : Introduction of spatial electron density distribution to the solvation theory

The authors propose the new generation of the reference interaction site model self-consistent field (RISM-SCF) method for the solvation effect on the electronic structure of a solute molecule, in which the procedure proposed by Gill et al. [J. Chem. Phys. 96, 7178 (1992)] is adopted. Main improvements are the introduction of spatial electron density distribution and the removal of the grid dependency that is inherent in the original RISM-SCF. The procedure also provides very stable determination of the effective charges even if a buried atom exists in the target molecule and eventually extends the applicability of the RISM-SCF. To demonstrate the superiority of our method, sample calculations for H2O, C2H5OH, and HLi in aqueous solution are presented.

Why Does Fluoride Anion Accelerate Transmetalation between Vinylsilane and Palladium(II)−Vinyl Complex? Theoretical Study

Transmetalation between palladium(II)-vinyl complex and vinylsilane was theoretically investigated with the DFT and MP2 to MP4 methods to clarify the reaction mechanism and the reasons why fluoride anion accelerates the Pd-catalyzed cross-coupling reaction between vinyl iodide and vinylsilane. This transmetalation occurs with a very large activation barrier (45.8 kcal/mol) and a very large endothermicity (25.6 kcal/mol) in the absence of fluoride anion, where the potential energy change resulting from the solvation effect is evident. This is consistent with the experimental fact that this cross-coupling reaction does not proceed well in the absence of fluoride anion. The effects of fluoride anion were investigated in three possible reaction courses. In the first course, fluorovinylsilicate anion is formed before the transmetalation, and it reacts with the palladium(II)-vinyl complex. In the second course, an iodo ligand is substituted for fluoride anion, and then the transmetalation occurs between the palladium(II)-fluoro-vinyl complex and vinylsilane. In the third course, fluoride anion attacks the Si center of vinylsilane in the transition state of the transmetalation between the palladium(II)-iodo-vinyl complex and vinylsilane. Our theoretical calculation suggests that fluorovinylsilicate anion is not formed in the case of trimethylvinylsilane. In the second and third cases, the transmetalation occurs with a moderate activation barrier (E(a)) and a considerably large exothermicity (E(exo)): E(a) = 25.3 kcal/mol and E(exo) = 5.7 kcal/mol in the second course, and E(a) = 12.7 kcal/mol and E(exo) = 24.8 kcal/mol in the third course, indicating that fluoride anion accelerates the transmetalation via the second and third reaction courses. The acceleration of transmetalation by fluoride anion is clearly interpreted in terms of the formation of a very strong Si-F bond and the stabilization of the transition state by the hypervalent Si center, which is induced by the fluoride anion. Our computational results show that hydroxide anion accelerates the transmetalation in a manner similar to that observed with fluoride anion. From these results, we predict that the electronegative anion accelerates this transmetalation because the electronegative group forms a strong covalent bond with the silyl group and facilitates the formation of the hypervalent Si center in the transition state.

Regioselective beta-metalation of meso-phosphanylporphyrins. Structure and optical properties of porphyrin dimers linked by peripherally fused phosphametallacycles.

meso-Diphenylphosphanylporphyrins were successfully prepared via Pd-catalyzed C-P cross-coupling reaction of the corresponding meso-iodoporphyrins with diphenylphosphane. The meso- phosphanylporphyrins underwent regioselective metalation at the beta carbon to produce novel classes of porphyrin dimers linked by peripherally fused phosphametallacycles. A Pd-mononucler complex was structurally characterized by X-ray crystallography, which revealed a flat structure of the Pd-linked porphyrin pi systems. Both experimental and theoretical results demonstrate that the orbital interaction between the pyrrolic ppi orbitals and the metal dpi orbital affects optical and electrochemical properties of the metal-linked coplanar porphyrin dimers.

Nickel-Catalyzed Double Carboxylation of Alkynes Employing Carbon Dioxide

The nickel-catalyzed double carboxylation of internal alkynes employing carbon dioxide (CO2) has been developed. The reactions proceed under CO2 (1 atm) at room temperature in the presence of a nickel catalyst, Zn powder as a reducing reagent, and MgBr2 as an indispensable additive. Various internal alkynes could be converted to the corresponding maleic anhydrides in good to high yields. DFT calculations disclosed the indispensable role of MgBr2 in the second CO2 insertion.

Thermal Degradation of Methyl beta-D-Glucoside. A Theoretical Study of Plausible Reaction Mechanisms

Thermal conversion of methyl beta-d-glucoside to levoglucosan was studied with the MP4//DFT(B3LYP) method. The first step is conformational change of the reactant to (1)C(4) from (4)C(1). The second step is intramolecular nucleophilic substitution at the anomeric C1, which occurs via one step without oxacarbenium ion intermediate. The DeltaG(0)() value (52.5 kcal/mol) is smaller than the C1-O1 bond energy, indicating the direct homolysis mechanism is clearly ruled out. Bimolecular reaction also occurs with smaller activation energy via the similar transition state.

Selective Formation and Efficient Photocurrent Generation of [70]Fullerene-Single-Walled Carbon Nanotube Composites

For the first time nanocarbon composites with C 70 molecules aligned on the sidewall of single-walled carbon nanotubes (SWNTs) are demonstrated. The C70-SWNT photoelectrochemical devices exhibit efficient photocurrent generation properties that result from selective formation of a single composite film consisting of a SWNT network covered with C70 molecules and high electron mobility through the C 70-SWNT network.