Co2(CO)8-mediated endo mode cyclization of epoxy-alcohol: synthesis of 2-ethynyl-3-hydroxy-2-methyltetrahydropyran and 2-ethynyl-3-hydroxy-3-methyltetrahydropyran derivatives

Successive treatment of 4,5-epoxy-5-methyl-7-trimethylsilyl-6-heptyne-1-ol with Co2(CO)8 at 0 degrees C and a catalytic amount of BF3 x OEt2 at -78 degrees C gave the tetrahydropyran derivatives with the cobalt-complexed moiety. Similarly 4,5-epoxy-4-methyl-7-trimethylsilyl-6-heptyne-1-ol underwent ring closure under the above conditions to provide the corresponding tetrahydropyran derivatives. The preferential endo mode cyclization over the exo one was observed in these experiments.     

1,6-dihydro-3(2H)-pyridinones as synthetic intermediates. Total synthesis of (±)-tecomanine

The first and stereoselective total synthesis of (±)-tecomanine ($\text{1}$) has been achieved from ethyl 1,6-dihydro-3(2H)-pyridinone-1-carboxylate ($\text{2}$) as a synthon.     

Novel metal-organic frameworks with specific topology from new tripodal ligands: 1,3,5-tris(1-imidazolyl)benzene and 1,3-bis(1-imidazolyl)-5-(imidazol-1-ylmethyl)benzene

Reactions of two new tripodal ligands 1,3,5-tris(1-imidazolyl)benzene (4) and 1,3-bis(1-imidazolyl)-5-(imidazol-1-ylmethyl)benzene (5) with metal [Ag(I), Cu(II), Zn(II), Ni(II)] salts lead to the formation of novel two-dimensional (2D) metal-organic frameworks [Ag(2)(4)(2)][p-C(6)H(4)(COO)(2)].H(2)O (6), [Ag(4)]ClO(4) (7), [Cu(4)(2)(H(2)O)(2)](CH(3)COO)(2).2H(2)O (8), [Zn(4)(2)(H(2)O)(2)](NO(3))(2) (9), [Ni(4)(2)(N(3))(2)].2H(2)O (10), and [Ag(5)]ClO(4) (11). All the structures were established by single-crystal X-ray diffraction analysis. Crystal data for 6: monoclinic, C2/c, a = 23.766(3) A, b = 12.0475(10) A, c = 13.5160(13) A, beta = 117.827(3) degrees, Z = 4. For compound 7: orthorhombic, P2(1)2(1)2(1), a = 7.2495(4) A, b = 12.0763(7) A, c = 19.2196(13) A, Z = 4. For compound 8: monoclinic, P2(1)/n, a = 8.2969(5) A, b = 12.2834(5) A, c = 17.4667(12) A, beta = 96.5740(10) degrees, Z = 2. For compound 9: monoclinic, P2(1)/n, a =10.5699(3) A, b = 11.5037(3) A, c = 13.5194(4) A, beta = 110.2779(10) degrees, Z = 2. For compound 10: monoclinic, P2(1)/n, a = 9.8033(3) A, b = 12.1369(5) A, c = 13.5215(5) A, beta = 107.3280(10) degrees, Z = 2. For compound 11: monoclinic C2/c, a = 18.947(2) A, b = 9.7593(10) A, c = 19.761(2) A, beta = 97.967(2) degrees, Z = 8. Both complexes 6 and 7 are noninterpenetrating frameworks based on the (6, 3) nets, and 8, 9 and 10 are based on the (4, 4) nets while complex 11 has a twofold parallel interpenetrated network with 4.8(2) topology. It is interesting that, in complexes 6,7, and 11 with three-coordinated planar silver(I) atoms, each ligand 4 or 5 connects three metal atoms, while in the case of complexes 8, 9, and 10 with six-coordinated octahedral metal atoms, each ligand 4 only links two metal atoms, and another imidazole nitrogen atom of 4 did not participate in the coordination with the metal atoms in these complexes. The results show that the nature of organic ligand and geometric needs of metal atoms have great influence on the structure of metal-organic frameworks.     

Synthesis and characterization of phosphorous-bridged bisphenoxy titanium complexes and their application to ethylene polymerization

Phosphorous-bridged bisphenoxy titanium complexes were synthesized and their ethylene polymerization behavior was investigated. Bis[3-tert-butyl-5-methyl-2-phenoxy](phenyl)phosphine tetrahydrofuran titanium dichloride (4a) was obtained by treatment of 3 equiv of n-BuLi with bis[3-tert-butyl-2-hydroxy-5-methylphenyl](phenyl)phosphine hydrochloride salt (3a) followed by TiCl₄(THF)₂ in THF. THF-free complexes 5a-5d were synthesized more conveniently by the direct reaction of MOM-protected ligands (2a-2d) with TiCl₄ in toluene. X-ray analysis of 4a revealed that the ligand is bonded to the octahedral titanium (IV) center in a facial fashion and two chlorine atoms possess cis-geometry. Complexes 4a and 5a-5d were utilized as catalyst precursors for ethylene polymerization. Complex 5c gave high molecular weight polyethylene (M_w = 1,170,000, M_w/M_n = 2.0) upon activation with Al(ⁱBu)₃/[Ph₃C][B(C₆F₅)₄] (TB). Ethylene polymerization activity of 5d activated with Al(ⁱBu)₃/TB reached 49.0 × 10⁶ g mol (cat) ⁻¹ h⁻¹.     

Preparation and characterization of silicalite-1 membranes prepared by secondary growth of seeds with different crystal sizes

MFI-type zeolite particles of 0.1–1 μm in diameter were prepared by adjusting tetra-n-propylammonium hydroxide (TPAOH) and water contents in synthesis mixtures. Using those particles as seeds, MFI-type zeolite membranes were prepared on the surface of a porous mullite tube by secondary growth. The membranes were formed as polycrystalline zeolite layers on and inside the porous support, and the membranes were composed of the [h 0 h]-oriented crystallites. The membrane consisting of a-oriented crystallites could be also prepared. However, the a-oriented zeolite layers were not active on the permeation properties of butanes. Rather the size and loaded amount of the seed particles influenced on the permeation properties through the membranes. As a result, the n-C₄H₁₀/i-C₄H₁₀ permselectivity could be increased to 220 by adjusting the size and the loaded amount of particles. These results suggest that the number of loaded particles affects on the permeation properties through the membranes.     

Thermal or Mechanical Stimuli‐Induced Photoluminescence Color Change of a Molecular Assembly Composed of an Amphiphilic Anthracene Derivative in Water

Molecular assemblies that change photoluminescence color in response to thermal or mechanical stimulation without dissociation into the monomeric states in water are described herein. A dumbbell‐shaped amphiphilic compound forms micellar molecular assemblies in water and exhibits yellow photoluminescence derived from excimer formation of the luminescent core, which contains a 2,6‐diethynylanthracene moiety. Annealing of the aqueous solution induces a photoluminescence color change from yellow to green (λ_{em, max}=558→525 nm). The same photoluminescence color change is also achieved by rubbing the yellow‐photoluminescence‐emitting molecular assemblies adsorbed on glass substrates with cotton wool in water. The observed green photoluminescence is ascribed to micelles that are distinct from the yellow‐photoluminescence‐emitting micelles, on the basis of transmission electron microscopy observations, atomic force microscopy observations, and dynamic light scattering measurements. We examined the relationship between the structure of the molecular assemblies and the photophysical properties of the anthracene derivative in water before and after thermal or mechanical stimulation and concluded that thermal or mechanical stimuli‐induced slight changes of the molecular‐assembled structures in the micelles result in the change in the photoluminescence color from yellow to green in water.     

Crystal structures and 77Se NMR spectra of molybdenum(IV) areneselenolates having intramolecular NH...Se hydrogen bonds

Salts of the monooxomolybdenum(IV,V) areneselenolates having intramolecular NH...Se hydrogen bonds, [Mo(IV)O(Se-2-RCONHC6H4)4]2- (R = t-Bu, CH3, CF3) and [Mo(V)O(Se-2-t-BuCONHC6H4)4]-, were synthesized and characterized by 1H nuclear magnetic resonance (NMR), 77Se NMR, electron spin resonance (ESR), UV-visible spectra, X-ray analysis, and electrochemical measurements. 77Se-1H correlated spectroscopy (COSY) indicated a significant correlation between amide 1H and selenolate 77Se atoms through an NH...Se hydrogen bond with 1J(77Se-1H) = 5.4 Hz coupling. The hydrogen bonds contribute to the positive shift in the Mo(V)/Mo(IV) redox potential. In the crystal structure of (PPh4)2[Mo(IV)O(Se-2-CH3CONHC6H4)4], an NH...O=Mo hydrogen bond was found. Ab inito calculations support the presence of intramolecular NH...O=Mo and NH...Se hydrogen bonds.     

Syntheses, structures, and photoluminescence properties of metal(II) halide complexes with pyridine-containing flexible tripodal ligands

Seven coordination compounds, [Zn(L3)Cl2] . MeOH . H2O (1), [Mn(L3)2Cl2] . 0.5EtOH . 0.5H2O (2), [Cu3(L2)2Cl6] . 2DMF (3), [Cu3(L2)2Br6] . 4MeOH (4), [Hg2(L4)Cl4] (5), [Hg2(L4)Br4] (6), and [Hg3(L4)2I6] . H2O (7), were synthesized by the reactions of ligands 1,3,5-tris(3-pyridylmethoxyl)benzene (L3), 1,3,5-tris(2-pyridylmethoxyl)benzene (L2), and 1,3,5-tris(4-pyridylmethoxyl)benzene (L4) with the corresponding metal halides. All the structures were established by single-crystal X-ray diffraction analysis. In complexes 1 and 2, L3 acts as a bidentate ligand using two of three pyridyl arms to link two metal atoms to result in two different 1D chain structures. In complexes 3 and 4, each L2 serves as tridentate ligand and connects three Cu(II) atoms to form a 2D network structure. Complexes 5 and 6 have the same framework structure, and L4 acts as a three-connecting ligand to connect Hg(II) atoms to generate a 3D 4-fold interpenetrated framework, while the structure of complex 7 is an infinite 1D chain. The results indicate that the flexible ligands can adopt different conformations and thus can form complexes with varied structures. In addition, the coordination geometry of the metal atom and the species of the halide were found to have great impact on the structure of the complexes. The photoluminescence properties of the complexes were investigated, and the Zn(II), Mn(II) and Hg(II) complexes showed blue emissions in solid state at room temperature.     

Synthesis and Crystal Structure of Blue Luminescent Cadmium(II) Coordination Networks with 4,4′-Bis(imidazol-1-ylmethyl)biphenyl from Different Solvent Systems

Two supramolecular complexes, [Cd(bimb)²Cl²] (1) and [Cd(bimb)(DMF)Cl²]·DMF (2) [bimb=4,4′-bis(imidazol-1-ylmethyl)biphenyl], were synthesized by reactions of CdCl²·2.5H²O with bimb ligand in ethanol and N,N′-dimethylformamide (DMF), respectively, and their structures were determined by X-ray crystallography. Complex 1 is an infinite 2D grid network bridged by bimb ligands, and the 2D sheets were further linked by C–H ?Cl hydrogen bonds to form a polycatenated 3D framework. Complex 2 has dicadmium(II) di-μ-chloride units which are connected by bimb bridging ligands to form an infinite non-interpenetrating 2D network. The results provide a nice example of the solvent system exerting a great effect on the construction of supramolecular frameworks.