The hydrogen salicylate ion as ligand. Complex formation equilibria with dioxouranium (VI), neodymium (III) and lead (II)

The complexation equilibria of the hydrogen salicylate ion, HL(-), have been studied, at 25 degrees C, by potentiometric measurements with a glass electrode in 1 M NaClO4 for uranyl and Nd(III) ions and in 3 M NaClO4 for Pb(II) ion. The ligand concentration (CL) was varied between 10(-3) and 0.05 M. In the system with U(VI) the concentrations ranged between: 10(-3) < or = [U(VI)] < or = 0.01 M, 0.5 < or = CL /[U(VI)] < or = 10 and 10(-2) < or = [H+] < or = 10(-5) M; for neodymium system: 2 x 10(-3) < or = [Nd(III)] < or = 0.01, 1 < or = CL /[Nd(III)] < or = 10 and 10(-2) < or = [H+] < or = 10(-7) M; for lead system: 10(-3) < or = [Pb(II) < or = 3 x 10(-3), 1 < or = CL /Pb(II)] < or = 2 and 10(-5) < or = [H+] < or = 10(-7.3) M. The experimental data have been explained with the formation of UO2HL+, UO2L, UO2(OH)L(-), (UO2)2(OH)L2(-) UO2(HL)L(-), NdHL(2+), NdL(+), Nd(OH)L, PbHL(+), PbL and PbL2(2-). Equilibrium constants are given for the investigated ionic media and at infinite dilution.     

Reaction of 3,4-disubstituted 1,2,5-oxadiazole 2-oxides with dipolarophiles : Substituent and solvent effect on the reaction courses

A variety of symmetrically or unsymmetrically 3,4-disubstituttd furoxans such as dicyano, dialkyl, diacyl, bis(phenylsulfonyl), N.N'-dialkyldicarbamoyl, 3(or 4)-methyl-4(or -3)-phenyl(or nitro, ethoxy, phenoxy, phenylthio, pyrrolidinyl, phenylsulfonyl), 3(or 4)-ethyl-4(or -3)phcnyl, and 3(or 4)-ethoxy-4(or -3)-phenylsulfonylruroxan reacted with dipolarophiles in toluene or xylene at the refluxing temperature to give nitrone-type 1,3-dipolar cycloadducts, 5-substituted 1-aza-2,8-dioxabicyclo-[3.3.0]octanes and/or 3-substituted 2-isoxazoline 2-oxides. On the other hand, some of the furoxans gave 2-isoxazolines via nitrile oxide 1,3-dipolar cycloaddition in a toluene (or xylene)-DMF solvent at the refluxing temperature.     

Solid state reaction synthesis of filled skutterudite compounds (Ce or Y)yFexCo4-xSb12 and the effect of filling atoms Ce or Y on lattice thermal conductivity

The synthesis of filled skutterudite compounds (Ce or Y)_y(Fe)_x(Co)_(4x)(Sb)_(12), through a solidstate reaction using chloride of Ce or Y,high purity powder of Co, Fe, and Sb as starting materials,was investigated. (Ce or Y)_y(Fe)_x(Co)_(4x)(Sb)_(12) (x=0--1.0, y=0--0.15) compounds were obtained at850--1 123 K. The results of Rietveld analysis demonstrate that (Ce or Y)_y(Fe)_x(Co)_(4x)(Sb)_12synthesized by a solid state reaction possesses a filled skutterudite structure. The filling fraction ofCe or Y obtained by Rietveld analysis agrees well with the composition obtained by chemicalanalysis. The lattice constant of (Ce)_y(Fe)_x(Co)_(4x)(Sb)_(12) increases with increasing substitution of Fe at Cosites, and with an increasing Ce filling fraction in the Sb-dodecahedron voids. The lattice thermalconductivity of (Ce or Y)_y(Fe)_x(Co)_(4x)(Sb)_(12) decreases significantly with an increasing Ce or Y fillingfraction in the voids and with substitution of Fe at Co sites.     

Stacking design of inverse perovskites: the systems (Sr3-xBaxN)E, E = Bi, Sb

The first representatives of 4H (BaMnO3-type structure, P63/mmc, Z = 4) and 9R (BaMnO3-type structure, Rm, Z = 9) inverse Perovskite phases are presented. The phases are obtained within the solid solutions (Sr3-xBaxN)E with E = Bi, Sb. The crystal structures and homogeneity ranges were studied by combined X-ray and neutron diffraction as well as chemical analyses. The cubic Perovskite phase with Bi (Sb) is stable in the range of 0.00 < or = x < or = 0.90(5) (0.00 < or = x < or = 1.30(5)), the 4H variant is stable for 1.55(5) < or = x < or = 2.10(5) (1.85(5) < or = x < or = 2.45(5)), the 9R structure is stable for 2.50(2) < or = x < or = 2.55(2) (2.56(2) < or = x < or = 2.60(2)), and the 2H phase is stable for 2.75(5) < or = x < or = 3.00 (2.80(5) < or = x < or = 3.00). Ba occupies preferable sites in the hexagonal stacking of close packed layers of alkaline earth metal ions and E3-; Sr is mainly located in cubic stacked layers. The phase order upon going from cubic (Sr3N)E to 2H-type (Ba3N)E concomitant to the pronounced Sr/Ba partial order can, in general, be rationalized considering the Coulomb repulsion of nitride ions, as well as the size and charge density of the alkaline earth metal ions.     

Group 6 imido complexes supported by diamido-donor ligands

Reactions of the lithiated diamido-pyridine or diamido-amine ligands Li(2)N(2)N(py) or Li(2)N(2)N(am) with [W(NAr)Cl(4)(THF)] (Ar = Ph or 2,6-C(6)H(3)Me(2); THF = tetrahydrofuran) afforded the corresponding imido-dichloride complexes [W(NAr)(N(2)N(py))Cl(2)] (R = Ph, 1, or 2,6-C(6)H(3)Me(2), 2) or [W(NAr)(N(2)N(am))Cl(2)] (R = Ph, 3, or 2,6-C(6)H(3)Me(2), 4), respectively, where N(2)N(py) = MeC(2-C(5)H(4)N)(CH(2)NSiMe(3))(2) and N(2)N(am) = Me(3)SiN(CH(2)CH(2)NSiMe(3))(2). Subsequent reactions of 1 with MeMgBr or PhMgCl afforded the dimethyl or diphenyl complexes [W(NPh)(N(2)N(py))R(2)] (R = Me, 5, or Ph, 6), respectively, which have both been characterized by single crystal X-ray diffraction. Reactions of Li(2)N(2)N(py) or Li(2)N(2)N(am) with [Mo(NR)(2)Cl(2)(DME)] (R = (t)Bu or Ph; DME = 1,2-dimethoxyethane) afforded the corresponding bis(imido) complexes [Mo(NR)(2)(N(2)N(py))] (R = (t)Bu, 7, or Ph, 8) and [Mo(N(t)Bu)(2)(N(2)N(am))] (9).     

Stereoselective generation of (E)- and (Z)-2-fluoroalkylidene-type carbenoids from (2-fluoro-1-alkenyl)iodonium salts and their application for stereoselective synthesis of fluoroalkenes

Alkylidene-type carbenoids, generated from (Z)- or (E)-(2-fluoro-1-alkenyl)iodonium salts by treatment with LDA, reacted with trialkylboranes to give (E)- or (Z)-(fluoroalkenyl)boranes stereoselectively. The resulting (fluoroalkenyl)borane can be used for the selective synthesis of (E)- or (Z)-fluoroalkenes, (E)- or (Z)-fluoroiodoalkenes, and alpha-fluoroketones. [reaction: see text]     

Regioselective rapid analog synthesis of 1,3-(or 1,5-)diphenyl-4-aryl/heteroaryl-5-(or 3-)(methylthio)pyrazoles via Suzuki cross-coupling

Regioselective routes for the synthesis of 1,3-(or 1,5-)diphenyl-4-aryl/heteroaryl-5-(or 3-)(methylthio)pyrazoles via Suzuki cross-coupling of 4-bromo (or 4-iodo)-1,3-(or 1,5-)diphenyl-5-(or 3-)(methylthio)pyrazoles have been reported.     

Stereochimie d'heterocycles du groupe IVB—II : Syntheses stereoselectives d'hydrogeno-1 et d'alkyl-1 sila-1 cyclobutanes

The reaction between n-butyllithium and 1,2 (or 1,3)-dimethyl-1-t-butoxy-1-silacyclobutanes proceeds with retention of configuration at silicon, and yields 10/90 (or 80/20) Z/E mixture of 1,2 (or 1,3)-dimethyl-1-n-butyl-1-silacyclobutanes. Methylation of 2 (or 3)-methyl-1-t-butoxy-1-silacyclobutanes (Z/E = 15/85 or 65/35) by methylmagnesium iodide gives 15/85 (or 65/35) Z/E mixture of 1,2 (or 1,3)-dimethyl-1-silacyclobutanes. The proposed configurations for substituted silacyclobutanes are supported by spectroscopic data (RMN) and chemical results (correlation of configuration and stereomutation of hydrogenosilacyclobutanes).     

Diastereoselective preparation and characterization of ruthenium bis(bipyridine) sulfoxide complexes

A new concept in the synthesis of optically active octahedral ruthenium complexes was realized for the first time when cis- or trans-Ru(bpy)2Cl, (cis- or trans-1) was reacted with either (R)-(+)- or (S)-(-)-methyl p-tolyl sulfoxide (2 or 3); this novel asymmetric synthesis leads to the diastereoselective formation of the ruthenium bis(bipyridine) complex cis-delta-[Ru(bpy)2(2)Cl]Cl (4) (49.6% de) or cis-lambda-[Ru(bpy)2(3)Cl]Cl (5) (48.4% de), respectively. cis- or trans-Ru(dmbpy)2Cl2 (cis- or trans-6) (dmbpy = 4,4'-dimethyl-2,2'-bipyridine) also reacts with 2 or 3, leading to the diastereoselective formation of cis-delta-[Ru(dmbpy)2(2)Cl]Cl (7) (59.5% de) or cis-lambda-[Ru(dmbpy)2(3)Cl]Cl (8) (57.2% de), respectively. The diastereoselectivity of these reactions is governed solely by the chirality of the sulfoxide nucleophile. This represents the first process by which a sigma-bonded ligand occupying only a single coordination site has had such an important influence on the stereochemical outcome of a ruthenium bis(bipyridine) complex formation. These novel complexes were fully characterized by elemental analysis and IR, UV/vis, and 1H, 13C, and 2D NMR spectroscopy. An investigation into the chiroptical properties of these novel ruthenium bis(bipyridine) sulfoxide complexes has been carried out, and circular dichroism spectra are used to assign absolute stereochemistry.     

The role of palladium catalyst and base in stereoselective transformations of (E)-2-chlorovinylsulfides

Stereoselective transformations of 2-chlorovinylsulfides in the presence of soluble (t-BuOK) or insoluble (solid KOH or Cs₂CO₃/18-crown-6) base and palladium catalyst (dppb)Pd(OAc)₂ have been studied. Depending on the substrate or catalytic system, the reaction leads to the formation of (E)-1,2-bis[aryl(or arylmethyl)thio]ethenes and/or (E)-1,4-bis[aryl(or arylmethyl)thio]-1-buten-3-ynes in yields of up to 93%.     

Effect of surfactants on the stability of thin liquid film flow on a rotating disk

The effect of surfactants on surface instabilities of thin liquid film flow on a rotating disk was studied at different flow rates Q (0.5相似文献   

Reaction of isopropylidene malonate with N-arylidene-1(or 2)-naphthylamines

The initial step in the reaction of isopropylidene malonate with N-arylidene-1(or 2)-naphthylamines is cleavage of the latter. The reaction gives isopropylidene 2-arylidene malonates, which subsequently react with α(or β)-naphthylamines to give 4-aryl-2-oxo-1,2,3,4-tetrahydro-7,8(or 5,6)-benzoquinolines. The latter are also obtained in the reaction of arylbis (isopropylidenemalonatyl)methanes with α(or β)-naphthylamines. Indane-1,3-dione and dimedone also cleave N-arylidene-1(or 2)-naphthylamines, and 2-arylideneindane-1,3-diones or arylbis (dimedonyl) methanes are obtained.     

Synthesis and structures of beta-diketiminatotin(II) halides, an amide and of Sn(=E)[{N(R)C(Ph)}2CH](NR2) (E = S or Se, R = SiMe3)

Treatment of [Li(L1)]2 (1) or K(L2) (2) with SnX2 in Et2O yielded the heteroleptic beta-diketiminatotin(II) halides Sn(L1)Cl (3a), Sn(L1)Br (3b) or Sn(L2)Cl (4), even when an excess of the alkali metal beta-diketiminate was used [L1={N(R)C(Ph)}2CH, L2={N(R)C(Ph)CHC(But)N(R)}, R = SiMe3]. From and half an equivalent each of SnCl2.2H2O and SnCl2, or one equivalent of SnCl2.2H2O, the product was Sn(L3)Cl (5) or Sn(L4)Cl (6), in which one or both of the N-R bonds of L1 had been hydrolytically cleaved; the compound Sn(L5)Cl (7) was similarly obtained from and an equivalent portion of SnCl2.2H2O [L3={N(R)C(Ph)CHC(But)N(H)}, L4={N(H)C(Ph)CHC(But)N(H)} and L5={N(H)C(Ph)}2CH]. The halide exchange between 3a and 3b, studied by two-dimensional (119)Sn{1H}-NMR spectroscopy, is attributed to implicate a (mu-Cl)(mu-Br)-dimeric intermediate or transition state. The 13C{1H}-NMR spectra of or showed two distinct resonances for each group, which coalesced on heating, corresponding to DeltaG(338 K)= 69.4 (3a) or 72.8 (3b) kJ mol(-1). The chloride ligand of was readily displaced by treatment with NaNR2, CF3SO3H or CH2(COPh)2, yielding Sn(L1)X [X = NR2 (8), O3SCF3 (9) or {OC(Ph)}2CH (10)]. Oxidative addition of sulfur or selenium to gave the tin(IV) terminal chalcogenides Sn(E)(L1)(NR2)[E = S (11) or Se (12)]. The X-ray structures of the cocrystal of 3a/3b and of the crystalline compounds 5, 6, 8, 11 and are presented, as well as multinuclear NMR spectra of each of the new compounds.     

Neutron scattering studies of K(3)H(SO(4))(2) and K(3)D(SO(4))(2): The particle-in-a-box model for the quantum phase transition

In the crystal of K(3)H(SO(4))(2) or K(3)D(SO(4))(2), dimers SO(4)???H???SO(4) or SO(4)???D???SO(4) are linked by strong centrosymmetric hydrogen or deuterium bonds whose O???O length is ≈2.50 A?. We address two open questions. (i) Are H or D sites split or not? (ii) Is there any structural counterpart to the phase transition observed for K(3)D(SO(4))(2) at T(c) ≈ 85.5 K, which does not exist for K(3)H(SO(4))(2)? Neutron diffraction by single-crystals at cryogenic or room temperature reveals no structural transition and no resolvable splitting of H or D sites. However, the width of the probability densities suggest unresolved splitting of the wavefunctions suggesting rigid entities H(L1∕2) -H(R1∕2) or D(L1∕2) -D(R1∕2) whose separation lengths are l(H) ≈ 0.16 A? or l(D) ≈ 0.25 A?. The vibrational eigenstates for the center of mass of H(L1∕2) -H(R1∕2) revealed by inelastic neutron scattering are amenable to a square-well and we suppose the same potential holds for D(L1∕2) -D(R1∕2). In order to explain dielectric and calorimetric measurements of mixed crystals K(3)D((1 - ρ))H(ρ)(SO(4))(2) (0 ≤ ρ ≤ 1), we replace the classical notion of order-disorder by the quantum notion of discernible (e.g., D(L1∕2) -D(R1∕2)) or indiscernible (e.g., H(L1∕2) -H(R1∕2)) components depending on the separation length of the split wavefunction. The discernible-indiscernible isostructural transition at finite temperatures is induced by a thermal pure quantum state or at 0 K by ρ.     

Novel 1,2,4-Triphosphole, 1,2,3-Triphosphetene and Azaphospholene Derivatives from N -Heterocyclic Carbenes and Phosphaalkynes

The stable singlet carbenes N,N '-bis(2,2-dimethylpropyl)-benzimidazolin-2-ylidene 1 and 1,3,4,5-tetramethylimidazol-2-ylidene 2 react with phosphaalkynes P L C-- t Bu ( 3a ) or P L C--N i Pr 2 ( 3b ) regioselective to give the aromatic 1,2,4-triphosphole derivatives ( 1 or 2 + 3a M 6a or 6b , respectively) or 1,2,3-triphosphetene ( 1 + 3b M 7 ) or azaphospholene ( 2 + 3b M 9 ) in almost quantitative yields. The mechanisms of the surprising formation of compound 9 under C--H-activation was studied by quantum chemical DFT calculations.     

Chemoenzymatic synthesis of sacranosides a and B

Direct beta-glucosidation between (-)-myrtenol and nerol and D-glucose (3) using the immobilized beta-glucosidase from almonds with the synthetic prepolymer ENTP-4000 gave myrtenyl O-beta-D-glucoside (4) and neryl O-beta-D-glucoside (10), respectively. The coupling of the myrtenyl or neryl O-beta-D-glucopyranoside congeners (7 or 13) and 2,3,4-tri-O-benzoyl-beta-L-arabinopyranosyl bromide (8) afforded the coupled products (9 or 14), respectively. Deprotection of the coupled products (9 or 14) afforded the synthetic myrtenyl 6-O-alpha-L-arabinopyranosyl-beta-D-glucopyranoside (Sacranoside A, 1) or neryl 6-O-alpha-L-arabinopyranosyl-beta-D-glucopyranoside (Sacranoside B, 2), respectively.     

A computational study of the lowest singlet and triplet states of neutral and dianionic 1,2-substituted icosahedral and octahedral o-carboranes

This work introduces a calibrated B3LYP/6-31G(d) study on the electronic structure of singlet and triplet neutral species of 1,2-substituted icosahedral 1,2-R(2)-1,2-C(2)B(10)H(10) and octahedral 1,2-R(2)-1,2-C(2)B(4)H(4) molecules with R = {H, OH, SH, NH(2), PH(2), CH(3), SiH(3)} and their respective dianions formed by proton removal on each R group. A variety of small adiabatic singlet-triplet gaps DeltaE(ST) are obtained from these systems ranging from 2.93 eV (R = NH(2)) 相似文献   

Synthesis of enantiopure (alphaS,betaS)- or (alphaR,betaS)-beta-amino alcohols by complete regioselective opening of aminoepoxides by organolithium reagents LiAlH4 or LiAlD4

The reaction of chiral (2R,1'S)- or (2S,1'S)-2-(1-aminoalkyl)epoxides, 1 or 2 with a variety of organolithium compounds to obtain the corresponding (alphaS,betaS)- or (alphaR,betaS)- beta-amino alcohols in enantiopure form is reported. In both cases, the opening of the oxirane ring at C-3 proceeded with total regioselectivity. Moreover, the ring opening of aminoepoxides 1 or 2 by hydride (utilizing LiAlH4) to obtain the corresponding (2S,3S)- or (2R,3S)-3-aminoalkan-2-ols is also described. The reaction of 1 or 2 with LiAlD4 in place of LiAlH4 gave the corresponding (2S,3S)- or (2R,3S)-3-amino-1-deuterioalkan-2-ols.     

基于环糊精包结络合作用的大分子自组装

本文综述了基于环糊精包结络合作用的大分子自组装的研究进展,包括：（1) 线型、梳型、多臂星型或超支化聚合物与环糊精或其二聚体自组装形成多聚轮烷（分子项链）、多聚准轮烷、双多聚（准）轮烷、分子管、双分子管、超分子凝胶及其应用;（2）桥联环糊精与桥联客体分子自组装制备线型或超支化超分子聚合物;（3）温度、pH值、光及客体分子刺激响应智能体系; （4) 通过亲水性的环糊精线型均聚物与含金刚烷的疏水性聚合物之间的包结络合作用来制备高分子胶束及其空心球等。     

Platinum complexes of naphthalene-1,8-dichalcogen and related polyaromatic hydrocarbon ligands

Platinum bisphosphine complexes bearing dichalcogen-derivatised naphthalene, acenaphthene or phenanthrene ligands have been prepared by either oxidative addition to zero-valent platinum species or from [PtCl(2)(PPhR(2))] (R=Ph or Me) and the disodium or dilithium salts of the parent disulfur, diselenide or mixed S/Se species. The parent naphthalene, acenaphthene and phenanthrene chalcogen compounds were treated with either [Pt(PPh(3))(4)] or [Pt(C(2)H(4))(PMe(3))(2)] (prepared in situ from [PtCl(2)(PMe(3))(2)], ethene and sodium naphthalide or super hydride [LiBEt(3)H]) to give the appropriate platinum(II) species. The dilithium salts of 1,8-E(2)-naphthalene (E=S or Se) prepared in situ by reduction of the E-E bond with [LiBEt(3)H] were treated with [PtCl(2)(PPh(3))(2)] to give [Pt(1,8-E(2)-nap)(PPh(3))(2)]. The tetraoxides [Pt(1,8-(S(O)(2))(2)-nap)(PR(3))(2)] (PR(3)=PPh(3) or PMe(2)Ph) were prepared in a similar metathetical manner from the appropriate [PtCl(2)(PR(3))] complexes and the disodium salt of naphthalene 1,8-disulfinic acid (1,8-(S(O)ONa)(2)-nap). The X-ray structures of selected examples reveal bidentate coordination with the naphthalene-E(2) unit hinged (111-137 degrees) with respect to the coordination plane. The naphthalene ring suffers significant distortion from planarity.