Synthesis of Arenethiolate Complexes of Divalent and Trivalent Lanthanides from Metallic Lanthanides and Diaryl Disulfides: Crystal Structures of [{Yb(hmpa)(3)}(2)(&mgr;-SPh)(3)][SPh] and Ln(SPh)(3)(hmpa)(3) (Ln = Sm, Yb; hmpa = Hexamethylphosphoric Triamide)

A convenient and one-pot synthetic method of lanthanide thiolate compounds was developed. An excess of metallic samarium, europium, and ytterbium directly reacted with diaryl disulfides in THF to give selectively Ln(II) thiolate complexes, [Ln(SAr)(&mgr;-SAr)(thf)(3)](2) (1, Ln = Sm; 2, Ln = Eu; Ar = 2,4,6-triisopropylphenyl), Yb(SAr)(2)(py)(4) (3, py = pyridine), and [{Ln(hmpa)(3)}(2)(&mgr;-SPh)(3)][SPh] (6, Ln = Sm; 7, Ln = Eu; 8, Ln = Yb; hmpa = hexamethylphosphoric triamide). Reaction of metallic lanthanides with 3 equiv of disulfides afforded Ln(III) thiolate complexes, Ln(SAr)(3)(py)(n)()(thf)(3)(-)(n)() (9a, Ln = Sm, n = 3; 9b, Ln = Sm, n = 2; 10, Ln = Yb, n = 3) and Ln(SPh)(3)(hmpa)(3) (11, Ln = Sm; 12, Ln = Eu; 13, Ln = Yb). Thus, Ln(II) and Ln(III) thiolate complexes were prepared from the same source by controlling the stoichiometry of the reactants. X-ray analysis of 8 revealed that 8 has the first ionic structure composed of triply bridged dinuclear cation and benezenethiolate anion [8, orthorhombic, space group P2(1)2(1)2(1) with a = 21.057(9), b = 25.963(7), c = 16.442(8) ?, V = 8988(5) ?(3), Z = 4, R = 0.040, R(w) = 0.039 for 5848 reflections with I > 3sigma(I) and 865 parameters]. The monomeric structures of 11 and 13 were revealed by X-ray crystallographic studies [11, triclinic, space group P&onemacr; with a = 14.719(3), b = 17.989(2), c = 11.344(2) ?, alpha = 97.91(1), beta = 110.30(2), gamma = 78.40(1) degrees, V = 2751.9(9) ?(3), Z = 2, R = 0.045, R(w) = 0.041 for 7111 reflections with I > 3sigma(I) and 536 parameters; 13, triclinic, space group P&onemacr; with a = 14.565(2), b = 17.961(2), c = 11.302(1) ?, alpha = 97.72(1), beta = 110.49(1), gamma = 78.37(1) degrees, V = 2706.0(7) ?(3), Z = 2, R = 0.031, R(w) = 0.035 for 9837 reflections with I > 3sigma(I) and 536 parameters]. A comparison with the reported mononuclear and dinuclear lanthanide thiolate complexes has been made to indicate that the Ln-S bonds weakened by the coordination of HMPA to lanthanide metals have ionic character.     

Photophysical and (photo)electrochemical properties of a coumarin dye

A new coumarin dye, cyano-{5,5-dimethyl-3-[2-(1,1,6,6-tetramethyl-10-oxo-2,3,5,6-tetrahydro-1H,4H,10H-11-oxa-3a-aza-benzo[de]anthracen-9-yl)vinyl]cyclohex-2-enylidene}-acetic acid (NKX-2753), was prepared and characterized with respect to photophysical and electrochemical properties. It was employed as a dye sensitizer in dye-sensitized solar cells and showed efficient photon-to-electron conversion properties. The photocurrent action spectrum exhibited a broad feature with a maximum incident photon-to-electron conversion efficiency (IPCE) of 84% at 540 nm, which is comparable to that for the famous red dye RuL2(NCS)2 (known as N3), where L stands for 2,2'-bipyridyl-4,4'-dicarboxylic acid. The sandwich-type solar cell with NKX-2753, under illumination of full sun (AM1.5, 100 mW cm(-2)), produced 16.1 mA cm(-2) of short-circuit photocurrent, 0.60 V of open-circuit photovoltage, and 0.69 of fill factor, corresponding to 6.7% of overall energy conversion efficiency using 0.1 M LiI, 0.05 M I2, 0.1 M guanidinium thiocyanate, and 0.6 M 1,2-dimethyl-3-n-propyl-imidazolium iodide in dry acetonitrile as redox electrolyte. In comparison with its analogue NKX-2586 (Langmuir 2004, 20, 4205), NKX-2753 with an extra side ring on the alkene chain produced much higher IPCE values at the same conditions. The side ring acted as a spacer to efficiently prevent dye aggregation when adsorbed on the TiO2 surface, resulting in significant improvements of short-circuit photocurrent, open-circuit photovoltage, and fill factor compared with NKX-2586 that aggregated on the TiO2 surface.     

Synthesis of [18,19,21,22‐13C4]‐Labeled Tautomycin as an NMR Probe of Protein Phosphatase Inhibitor

We have accomplished the synthesis of ¹³C‐labeled tautomycin at the C18, C19, C21, and C22 positions starting from 100 % [¹³C]triethylphosphonoacetate for the purpose of elucidating the dynamics and conformation of the C17–C26 moiety. NMR spectroscopy of ¹³C‐labeled tautomycin revealed strong binding with protein phosphatase type 1 and new features in the ¹³C NMR spectrum, such as the very small three‐bond coupling constants (²J).     

A study on the conformation-anomeric effect-stereoselectivity relationship in anomeric radical reactions,using conformationally restricted glucose derivatives as substrates

We previously theorized that, since the stereoselectivity of anomeric radical reactions is significantly influenced by the kinetic anomeric effect, which can be controlled by restricting the conformation of the radical intermediate, the proper conformational restriction of the pyranose ring of the substrates would therefore make highly alpha- and beta-stereoselective anomeric radical reactions possible. This theory was based on our previous results of the anomeric radical reactions with d-xylose derivatives as the substrates. We herein report the anomeric radical deuteration reactions with the conformationally restricted 1-phenylseleno-d-glucose derivatives, 2g and 3g, restricted in a (4)C(1)-conformation by an O-cyclic diketal moiety, and 4g, 5g, 6g, 7g, and 8g, restricted in a (1)C(4)-conformation by bulky O-silyl protecting groups. The radical deuterations with Bu(3)SnD, using the (4)C(1)-restricted substrates 2g and 3g, afforded the corresponding alpha-products (alpha/beta = 98:2) highly stereoselectively, whereas the (1)C(4)-restricted substrate 6g, having a trigonal (sp(2)) carbon substituent, i.e., -CHO, at the 5-position, selectively gave the beta-products (alpha/beta = 0:100). Thus, the stereoselectivity was significantly increased by the conformational restriction and was completely inverted by changing the substrate conformation from the (4)C(1)-form to the (1)C(4)-form. On the other hand, the deuterations with the (1)C(4)-restricted substrates 4g and 5g showed that the 1,5-steric effect due to the tetrahedral carbon substituent (-CH(2)OTIPS or -CH(2)OH) at the 5-axial position dominantly prevented the hydride transfer from the beta-face competing with the kinetic anomeric effect. This study suggests that, depending on the restricted conformation of the substrates to the (4)C(1)- or the (1)C(4)-form, the alpha- or beta-products would be obtained highly stereoselectively via anomeric radical reactions of hexopyranoses.     

Studies on furan derivatives. V. A novel ethoxycarbonylmethylation of the 5-nitro-2-furan ring in the reaction of α-(2-furyl)-β-(5-nitro-2-furyl)ethynyl with N-ethoxycarbonylmethylpyridinium ylide

An unexpected product, 1-(4-ethoxycarbonylmethyl-5-nitro-2-furyl)-2-(2-furyl)-3-ethoxycarbonyl-indolizine was obtained by the reaction of α-(2-furyl)-β-(5-nitro-2-furyl)ethynyl with N-ethoxy-carbonylmethylpyridinium ylide in N,N-dimethylformamide, together with 1-(5-nitro-2-furyl)-2-(2-furyl)-3-ethoxycarbonylindolizine.     

Cloud point extraction equilibrium of lanthanum(III), europium(III) and lutetium(III) using di(2-ethylhexyl)phosphoric acid and Triton X-100

The cloud point extraction behaviors of lanthanoids(III) (Ln(III) = La(III), Eu(III) and Lu(III)) with and without di(2-ethylhexyl)phosphoric acid (HDEHP) using Triton X-100 were investigated. It was suggested that the extraction of Ln(III) into the surfactant-rich phase without added chelating agent was caused by the impurities contained in Triton X-100. The extraction percentage more than 91% for all Ln(III) metals was obtained using 3.0 × 10⁻⁵ mol dm⁻³ HDEHP and 2.0% (v/v) Triton X-100. From the equilibrium analysis, it was clarified that Ln(III) was extracted as Ln(DEHP)₃ into the surfactant-rich phase. The extraction constant of Ln(III) with HDEHP and 2.0% (v/v) Triton X-100 were also obtained.     

Two-dimensional Monte Carlo simulations of a polydisperse colloidal dispersion composed of ferromagnetic particles for the case of no external magnetic field

We have investigated the aggregation phenomena in a polydisperse colloidal dispersion composed of ferromagnetic particles by means of the cluster-moving Monte Carlo method. The results have been compared with those for a monodisperse system. The internal structures of aggregates have been analyzed in terms of the radial distribution function in order to clarify the quantitative differences in the internal structures of clusters. In addition, the cluster size distribution and angular distribution function have been investigated. The results obtained in the present study are summarized as follows. In a monodisperse system, open necklacelike clusters are formed and they extend with increasing strength of the magnetic particle-particle interaction. In a polydisperse system with a small standard deviation in the particle size distribution, sigma=0.2, larger necklacelike clusters are formed and some looplike clusters can also be observed. In a polydisperse system with a larger standard deviation, sigma=0.35, clumplike clusters are formed for a weak magnetic particle-particle interaction. For a stronger magnetic interaction, larger size clusters that exhibit a complicated network structure are formed. These complicated cluster formations found in a polydisperse system are mainly due to the effect of the presence of larger particles.     

Self-crosslinkable polymers. I. Copolymerization of glycidyl methacrylate with 2-vinylpyridine and 2-vinyl-5-ethylpyridine

A soluble and self-crosslinkable linear copolymer with pendant epoxy and pyridyl groups was obtained from glycidyl methacrylate (M₁) and 2-vinylpyridine (M₂) or 2-vinyl-5-ethylpyridine (M₂) by the action of azobisisobutyronitrile. The monomer reactivity ratios were determined in tetrahydrofuran at 60°C: r₁ = 0.510, r₂ = 0.620 with 2-vinylpyridine and r₁ = 0.57, r₂ = 0.62 with 2-vinyl-5-ethylpyridine. These were consistent with the calculated values with the reported Q and e values for these monomers. The intrinsic viscosities of the copolymers with 2-vinylpyridine and with 2-vinyl-5-ethylpyridine were found to be 0.17–0.19 and 0.26–0.38, respectively, in tetrahydrofuran at 30°C; they were independent of the copolymer composition. The copolymers were amorphous, had no clear melting points, and became insoluble crosslinked polymers under heating without further addition of any curing agents.     

PREPARATION AND PROPERTY OF POLYMERIC PENDANT Ru(bpy)_3~(2+) COMPLEXES

Polymeric pendant Ru(bpy)_3~(2+) complexes were prepared from homopolymer and copolymers of 4-methyl-4'-vinyl-2,2'-bipyridine (Vbpy). Vbpy was prepared from 4-methylpyridine. The comonomers were styrene (St), acrylic acid (AA), N-vinylpyrrolidone (Pyr), 4-vinylpyridine (Vpy), methyl methacrylate (MMA), 2-hydroxyethyl methacrylate (HEMA), acrylonitrile (AN) and N-ethyl-4-vinylpyridium bromide (EQ-Vpy). The fraction of the pendant Ru(bpy)_3~(2+) repeating unit in the polymeric complex was 0.022 to 0.052. Absorption maximum, molar extinction coefficient, emission maximum and relative emission intensity of the polymeric complexes were studied.     

Synthetic studies directed toward the assembly of the C-glycoside fragment of the telomerase inhibitor D8646-2-6

[reaction: see text] Construction and characterization of the C-glycosidic moiety of telomerase inhibitor D8646-2-6 (1) are described. This is the first example of the C-glycosylation using electron-poor aromatics, 4-hydroxypyrone, as a glycosyl acceptor. The glycosylation reaction and base-promoted isomerization affords desired beta-C-glycoside in a 61% overall yield.