Modification of flexible part in Cu(2+) interdigitated framework for CH(4)/CO(2) separation

The structural flexibility of Cu(2+) interdigitated layer type framework was controlled and the compound represented clear separation property of CH(4)/CO(2) at range of 0-1.0 MPa and recovery of adsorbed CO(2) above 0.1 MPa.     

Separation of a Slater Determinant Wave Function with a Neck Structure into Spatially Localized Subsystems

A method of separating a Slater determinant wave function with a two-center neck structure into spatially localized subsystems is proposed, and it is applied to α + α Margenau–Brink cluster wave functions and antisymmetrized molecular dynamics wave functions of the ground state in ¹⁰Be and a negative-parity largely deformed state in ³⁵S.     

Reaction of Titanium Isopropoxide with Alkanolamines and Association of the Resultant Ti Species

A clear alcoholic solution of titanium alkoxide with an addition of various alkanolamines is suitable for a sol-gel coating of titania films. The reaction of titanium isopropoxide, Ti(OPr ⁱ )₄ (TIP), with alkanolamines, such as triethanolamine (TEAH₃), diethanolamine (DEAH₂), and N-ethyldiethanolamine (EDEAH₂), and an association of the Ti species in the resultant mixtures were examined via liquid-state nuclear magnetic resonance (NMR), infrared spectroscopy (IR), and cryoscopy measurements. Regardless of the kinds of the alkanolamines used, the IR and NMR spectra showed that alcohol exchange reactions occurred between the alcoholic moieties in alkanolamines and the isopropoxy groups in TIP, and that the N atom in the alkanolamines might be datively bonded to Ti. In the DEAH₂ and EDEAH₂ systems with the molar ratio of amine/TIP = 1, the results of the NMR and cryoscopy measurements showed that an association degree of the formed Ti species increased with an increase in the concentration of TIP, according to the thermodynamical equilibriums of associations between various oligomers. The increase was larger in the DEAH₂ system than in the EDEAH₂ one, because of the larger equilibrium constants due to the smaller size of the DEA group. In the system of EDEAH₂/TIP = 2, the NMR spectra showed that only one kind of oligomer was formed as a Ti species, independent of the concentration of TIP. The oligomer may be a much more stable species than other species. The cryoscopy results showed that the oligomer had a tetrameric structure.     

Head-to-tail dimerization of acrylates catalyzed by iridium complexes

Head-to-tail dimerizations of acrylates and vinyl ketone were successfully performed by the use of iridium complexes in good yields. An iridium hydride complex generated in situ from [IrCl(cod)]2 and alcohols in the presence of Na2CO3 and (MeO)3P was found to be an active species promoting the head-to-tail dimerization of acrylates. Thus, butyl acrylate afforded the corresponding head-to-tail dimer in 86% yield.     

Enantio- and diastereoselective Michael reaction of 1,3-dicarbonyl compounds to nitroolefins catalyzed by a bifunctional thiourea

We synthesized a new class of bifunctional catalysts bearing a thiourea moiety and an amino group on a chiral scaffold. Among them, thiourea 1e bearing 3,5-bis(trifluoromethyl)benzene and dimethylamino groups was revealed to be highly efficient for the asymmetric Michael reaction of 1,3-dicarbonyl compounds to nitroolefins. Furthermore, we have developed a new synthetic route for (R)-(-)-baclofen and a chiral quaternary carbon center with high enantioselectivity by Michael reaction. In these reactions, we assumed that a thiourea moiety and an amino group of the catalyst activates a nitroolefin and a 1,3-dicarbonyl compound, respectively, to afford the Michael adduct with high enantio- and diastereoselectivity.     

Ruthenium complexes of easily accessible tridentate ligands based on the 2-aryl-4,6-bis(2-pyridyl)-s-triazine motif: absorption spectra, luminescence properties, and redox behavior

A family of tridendate ligands 1 a-e, based on the 2-aryl-4,6-di(2-pyridyl)-s-triazine motif, was prepared along with their hetero- and homoleptic Ru(II) complexes 2 a-e ([Ru(tpy)(1 a-e)](2+); tpy=2,2':6',2"-terpyridine) and 3 a-e ([(Ru(1 a-e)(2)](2+)), respectively. The ligands and their complexes were characterized by (1)H NMR spectroscopy, ES-MS, and elemental analysis. Single-crystal X-ray analysis of 2 a and 2 e demonstrated that the triazine core is nearly coplanar with the non-coordinating ring, with dihedral angles of 1.2 and 18.6 degrees, respectively. The redox behavior and electronic absorption and luminescence properties (both at room temperature in liquid acetonitrile and at 77 K in butyronitrile rigid matrix) were investigated. Each species undergoes one oxidation process centered on the metal ion, and several (three for 2 a-e and four for 3 a-e) reduction processes centered on the ligand orbitals. All compounds exhibit intense absorption bands in the UV region, assigned to spin-allowed ligand-centered (LC) transitions, and moderately intense spin-allowed metal-to-ligand charge-transfer (MLCT) absorption bands in the visible region. The compounds exhibit relatively intense emissions, originating from triplet MLCT levels, both at 77 K and at room temperature. The incorporation of triazine rings and the near planarity of the noncoordinating ring increase the luminescence lifetimes of the complexes by lowering the energy of the (3)MLCT state and creating a large energy gap to the dd state.     

First Ritter-type reaction of alkylbenzenes using N-hydroxyphthalimide as a key catalyst

The first Ritter-type reaction of alkylbenzenes with nitriles has been successfully achieved by the use of N-hydroxyphthalimide (NHPI) as a key catalyst. Thus, treatment of ethylbenzene with ammonium hexanitratocerate(IV) (CAN) in the presence of a catalytic amount of NHPI in EtCN under argon produced the corresponding amide in good selectivity.     

Enantioselective Michael reaction of malonates to nitroolefins catalyzed by bifunctional organocatalysts

Michael reaction of malonates to nitroolefins with chiral bifunctional organocatalysts, bearing both a thiourea and tertiary amino group, afforded Michael adducts with high yields and enantioselectivities (up to 95%, up to 93% ee).     

Synthesis and crosslinking behavior of a novel linear polymer bearing 1,2,3‐triazol and benzoxazine groups in the main chain by a step‐growth click‐coupling reaction

The click‐coupling reaction was applied to polycondensation, to synthesize a high‐molecular weight prepolymer having benzoxazine moieties in the main chain. For the polycondensation, a bifunctional N‐propargyl benzoxazine was synthesized from bisphenol A, propargylamine, and formaldehyde. The propargyl group was efficiently used for the copper(I)‐catalyzed alkyne‐azide “click” reaction with p‐xylene‐α,α′‐diazide, to give the corresponding linear polycondensate having 1,2,3‐triazole junctions. The polycondensation proceeded in N,N‐dimethylformamide (DMF) at room temperature. By this highly efficient “click‐” polycondensation reaction, the benzoxazine ring in the monomer was successfully introduced into the polymer main chain without any side reaction. The obtained polymer (=prepolymer) underwent thermal crosslinking to afford the corresponding product, which was insoluble in a wide range of organic solvents and exhibited higher thermal stability than the polymer before crosslinking. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 2316–2325, 2008