Synthesis and structures of Mo3Se7Te2Br10, Mo3Se7TeI6, and Mo6Te21I22 containing TeX3- (X=Br, I) ligands coordinated to a triangular cluster core

New ternary and quaternary molybdenum cluster chalcohalides were obtained by high-temperature reactions between Mo, chalcogens, and halogens in evacuated ampules. The crystal structures of [Mo3Se7(TeBr3)Br2]2[Te2Br10] (1), [Mo3Se7(TeI3)I2]I (2), and [Mo3Te7(TeI3)3]2(I)(TeI3) (3) were determined by single-crystal X-ray diffraction. The structures of 1 and 2 consist of positively charged zigzag chains infinity1 [Mo3Se7(TeX3)X4/2] (X=Br, I), with Te2Br102- and I-, respectively, as counterions. The TeI3- and TeBr3- ions function as bidentate ligands in 1 and 2. In 3, TeI3- is not coordinated to the metal but acts as a counterion to the [Mo3Te7(TeI3)3]+ cluster cation.     

对Niementowski反应的改进

在三氯氧磷存在下,以甲酰胺和邻氨基苯甲酸类化合物为原料,用改进的Niementowski反应合成了5种喹唑啉酮化合物：6-X-4(3H)-喹唑啉酮(X=NO2,Cl,Br,I)和1-(呋喃-2-甲基)-6-磺酰胺基-7-氯-4(1H)-喹唑啉酮,并对该反应的历程进行了初步探讨。     

Synthesis of carbaalane halogen derivatives

The carbaalane halogen derivatives [(AlX)(6)(AlNMe(3))(2)(CCH(2)CH(2)SiMe(3))(6)] (X = F (9), Cl (7), Br (10), I (11)) were prepared in toluene from [(AlH)(6)(AlNMe(3))(2)(CCH(2)CH(2)SiMe(3))(6)] (6) and BF(3).OEt(2), BX(3) (X = Br, I), Me(3)SnF, and Me(3)SiX (X = Cl, Br, I), respectively. A partially halogenated product [(AlH)(2)(AlX)(4)(AlNMe(3))(2)(CCH(2)CH(2)SiMe(3))(6)] (12) (X = Cl (approximately 40%), Br (approximately 60%)) was obtained from 5 and impure BBr(3). [(AlH)(6)(AlNMe(3))(2)(CCH(2)Ph)(6)] (5) was converted to [(AlX)(6)(AlNMe(3))(2)(CCH(2)Ph)(6)] (X = F (13), Cl (14), Br (15), I (16)) using BF(3).OEt(2) and Me(3)SiX (X = Cl, Br, I), respectively. The X-ray single-crystal structures of 11.C(6)H(6), 12.3C(7)H(8), 13.6C(7)H(8), and 15.4C(7)H(8) were determined. Compounds 7 and 9-11 are soluble in benzene/toluene and could be well characterized by NMR spectroscopy and MS (EI) spectrometry. The results demonstrate the facile substitution of the hydridic hydrogen atoms in 5 and 6 by the halides with different reagents.     

某些有机钨卤化物RC~5H~4(CO)~3WX(R=MeCO, MeO~2C, EtO~2C; X=Cl, Br, I)的合成及结构鉴定

通过酮基或酯基官能团取代的环戊二烯基(三羰基)钨钠 RC~5H~4(CO)~3WN(R=MeCO, MeO~2C, EtO~2C 与I~2、Px~3(X=Cl、Br、I), PhPCl~2, p-MeC~6H~4PCl~2或MeAsI~2 反应, 结果得到8个含相应官能团的有机钨卤化物。用X射线衍射法鉴定了其中 R=MeCO, X=Br的单晶分子结构, 晶体属单斜晶系, 空间群P~21。     

Syntheses, crystal structures, reactivity, and photochemistry of gold(III) bromides bearing N-heterocyclic carbenes

Gold(I) complexes bearing N-heterocyclic carbenes (NHC) of the type (NHC)AuBr (3a/3b) [NHC = 1-methyl-3-benzylimidazol-2-ylidene (= MeBnIm), and 1,3-dibenzylimidazol-2-ylidene (= Bn(2)Im)] are prepared by transmetallation reactions of (tht)AuBr (tht = tetrahydrothiophene) and (NHC)AgBr (2a/2b). The homoleptic, ionic complexes [(NHC)(2)Au]Br (6a/6b) are synthesized by the reaction with free carbene. Successive oxidation of 3a/3b and 6a/6b with bromine gave the respective (NHC)AuBr(3) (4a/4b) and [(NHC)(2)AuBr(2)]Br (7a/7b) in good overall yields as yellow powders. All complexes were characterized by NMR spectroscopy, mass spectrometry, elemental analysis and single crystal X-ray diffraction. Reactions of the Au(III) complexes towards anionic ligands like carboxylates, phenolates and thiophenolates were investigated and result in a complete or partial reduction to a Au(I) complex. Irradiation of the Au(III) complexes with UV light yield the Au(I) congeners in a clean photo-reaction.     

Hg3AsE4X (E = S, Se; X = Cl, Br, I), a family of isotypic compounds with an acentric, layered structure

Four isotypic compounds Hg3AsS4Cl, Hg3AsS4Br, Hg3AsSe4Br, and Hg3AsSe4I were synthesized in the quaternary system mercury/arsenic/chalcogen/halogen by vapor transport reactions from As, Hg(II) halide, Hg(II) chalcogenide, and elemental chalcogen at temperatures between 250 and 310 degrees C. Their structures were solved by single-crystal X-ray diffraction analyses. The compounds crystallize in the hexagonal system with the acentric space group P63mc and the following lattice parameters: a = 7.431(5) A, c = 9.003(8) A for Hg3AsS4Cl, a = 7.430(5) A, c = 9.364(5) A for Hg3AsS4Br, a = 7.707(8) A, c = 9.47(2) A for Hg3AsSe4Br, and a = 7.6902(7) A, c = 9.968(1) A for Hg3AsSe4I, and Z = 2. All compounds are air-stable and form hexagonal prismatic crystals. The colors vary from yellow (Hg3AsS4Cl) to red (Hg3AsSe4I). The structures consist of infinity 2[Hg3AsE4]+ polycationic layers built of six-membered Hg3E3 and Hg2AsE3 rings in chair and boat conformations. Alternatively, the structure of the layers can be described as composed of [AsE3]3- and [Hg3E]4+ ions both forming regular trigonal pyramids. The halide ions are intercalated between the layers and have only weak bonds to the mercury atoms. The acentricity of the structures was confirmed through SHG measurements using IR laser radiation (lambda = 1064 nm).     

Two- and three-body photodissociation dynamics of diiodobromide (I2Br-) anion

The photodissociation of gas-phase I(2)Br(-) was investigated using fast beam photofragment translational spectroscopy. Anions were photodissociated from 300 to 270 nm (4.13-4.59 eV) and the recoiling photofragments were detected in coincidence by a time- and position-sensitive detector. Both two- and three-body channels were observed throughout the energy range probed. Analysis of the two-body dissociation showed evidence for four distinct channels: Br(-) + I(2), I(-) + IBr, Br+I(2) (-), and I + IBr(-). In three-body dissociation, Br((2)P(3∕2)) + I((2)P(3∕2)) + I(-) and Br(-) + I((2)P(3∕2)) + I((2)P(3∕2)) were produced primarily from a concerted decay mechanism. A sequential decay mechanism was also observed and attributed to Br(-)((1)S)+I(2)(B(3)Π(0u) (+)) followed by predissociation of I(2)(B).     

Synthesis of 5-(1-azido-2-haloethyl)arabinouridines

A novel class of 5-(1-azido-2-haloethyl)arabinouridines 4–6 was synthesized by the regiospecific addition of halogenoazides (XN₃: X = C1, Br, I) to the vinyl substituent of 5-vinylarabinouridine (7). The title 5-(1-azido-2-haloethyl)arabinouridines 4–6 were previously shown to exhibit significant in vitro antiviral activity against herpes simplex virus type 1, varicella zoster virus and cytomegalo virus.     

四卤合金属酸十六铵的光电子能谱研究

用ＡｌＫａ（ｈ＝１４８６．６ｅＶ）Ｘ－射线测量１５种四卤合金属酸十六铵的光电子能谱。讨论了这些化合物的Ｚｎ２ｐ、Ｃｏ２ｐ、Ｍｎ２ｐ、Ｃｄ３ｄ、Ｃｌ２ｐ、Ｂｒ３ｄ、Ｉ３ｄ、Ｎ１ｓ的芯能级结合能的化学位移。根据Ｐａｕｌｉｎｇ电负性讨论了这些数据和计算电荷的关系。     

Enzymatic Synthesis of Dipeptide Derivatives Containing Non-coded Amino Acids in Organic Solvents

ＩｎｔｒｏｄｕｃｔｉｏｎＥｎｚｙｍａｔｉｃｐｅｐｔｉｄｅｓｙｎｔｈｅｓｉｓｈａｓｄｒａｗｎｍｕｃｈａｔｔｅｎ ｔｉｏｎｂｅｃａｕｓｅｏｆｉｔｓａｄｖａｎｔａｇｅｏｆｅｎｚｙｍｅｓｔｅｒｅｏｓｐｅｃｉｆｉｃｉｔｙ ,ｍｉｌｄｒｅａｃｔｉｏｎｃｏｎｄｉｔｉｏｎｓ ,ｍｉｎｉｍｕｍｓｉｄｅ ｃｈａｉｎｐｒｏｔｅｃｔｉｏｎａｎｄａｖｏｉｄａｎｃｅｏｆｒａｃｅｍｉｚａｔｉｏｎ .Ｂｕｔｔｈｅｓｔｒｉｃｔｓｕｂｓｔｒａｔｅｓｐｅｃｉｆｉｃｉｔｙｏｆｔｈｅｅｎｚｙｍｅｓｌｉｍｉｔｓｔｈｅｉｒａｐｐｌｉｃａｔｉｏｎｓ .…     

N,N-二烷基-α-卤磺酰基二氟乙酰胺的合成及性质研究

由于氟原子的独特性质, 含氟有机化合物,特别是含氟生物活性物质的合成,近来愈来愈引起人们的兴趣。利用卤代二氟乙酸酯(XCF_2CO_2R,X=Br、Ⅰ)在分子中引入CF_2基团已有不少报道,但其合成方法报道不多,且条件过于剧烈。本文从易得的全氟乙磺内酯出发,通过分解N,N-二烷基-α-卤磺     

A Mixed-valent Hexanuclear CuⅡ-CuⅠ Complex with Unusual Tridentate pbi Ligand (pbi= 2-(2-Pyridyl)-benzimidazole)

A mixed-valent hexanuclear complex [CuⅡCuⅠ2(pbi)2Br2]2 (pbi = (2-(2-pyridyl)-benzimidazole) exhibiting a dimeric unit bridged by two Br atoms was synthesized by hydrothermal reaction.Interestingly, there exist intramolecular and intermolecular π-πstacking interactions as well as metalaromatic ring interactions in the title complex. The crystal belongs to the monoclinic system, space group P-1, with a = 7.1061(9), b = 12.1008(13), c = 14.0711(17) (A), α = 91.742(8), β = 100.155(9), γ =90.486(7)°, V = 1190.3(2)(A)3, Z = 2, C48H32Br4Cu6N12, Mr = 1477.74, Dc= 2.061 g/cm3, F(000) = 718,μ(MoKα) = 6.039 mm-1, the final R = 0.0481 and wR = 0.0974 for 3426 observed reflections (I＞2σ(I)).     

Mononuclear Schiff base boron halides: synthesis, characterization, and dealkylation of trimethyl phosphate

A series of mononuclear boron halides of the type LBX(2) [LH = N-phenyl-3,5-di-tert-butylsalicylaldimine, X = Cl (2), Br (3)] and LBX [LH2 = N-(2-hydroxyphenyl)-3,5-di-tert-butylsalicylaldimine, X = Cl (7), Br (8); LH2 = N-(2-hydroxyethyl)-3,5-di-tert-butylsalicylaldimine, X = Cl (9), Br (10); and LH2 = N-(3-hydroxypropyl)-3,5-di-tert-butylsalicylaldimine, X = Cl (11), Br (12)] were synthesized from their borate precursors LB(OMe)2 (1) (LH = N-phenyl-3,5-di-tert-butylsalicylaldimine) and LB(OMe) [LH2 = N-(2-hydroxyphenyl)-3,5-di-tert-butylsalicylaldimine (4), N-(2-hydroxyethyl)-3,5-di-tert-butylsalicylaldimine (5), N-(3-hydroxypropyl)-3,5-di-tert-butylsalicylaldimine (6)]. The boron halide compounds were air and moisture sensitive, and upon hydrolysis, compound 7 resulted in the oxo-bridged compound 13 that contained two seven-membered boron heterocycles. The boron halide compounds dealkylated trimethyl phosphate in stoichiometric reactions to produce methyl halide and unidentified phosphate materials. Compounds 8 and 12 were found to be the most effective dealkylating agents. On reaction with tert-butyl diphenyl phosphinate, compound 8 produced a unique boron phosphinate compound LB(O)OPPh2 (14) containing a terminal phosphinate group. Compounds 1-14 were characterized by 1H, 13C, 11B, 31P NMR, IR, MS, EA, and MP. Compounds 5, 6, and 11-14 also were characterized by single-crystal X-ray diffraction.     

Tuning the HOMO energy levels of organic dyes for dye-sensitized solar cells based on Br-/Br3- electrolytes

A series of novel metal-free organic dyes TC301-TC310 with relatively high HOMO levels were synthesized and applied in dye-sensitized solar cells (DSCs) based on electrolytes that contain Br(-)/Br(3)(-) and I(-)/I(3)(-). The effects of additive Li(+) ions and the HOMO levels of the dyes have an important influence on properties of the dyes and performance of DSCs. The addition of Li(+) ions in electrolytes can broaden the absorption spectra of the dyes on TiO(2) films and shift both the LUMO levels of the dyes and the conduction band of TiO(2), thus leading to the increase of J(sc) and the decrease of V(oc). Upon using Br(-)/Br(3)(-) instead of I(-)/I(3)(-), a large increase of V(oc) is attributed to the enlarged energy difference between the redox potentials of electrolyte and the Fermi level of TiO(2), as well as the suppressed electron recombination. Incident photon to current efficiency (IPCE) action spectra, electrochemical impedance spectra, and nanosecond laser transient absorption reveal that both the electron collection yields and the dye regeneration yields (Φ(r)) depend on the potential difference (the driving forces) between the oxidized dyes and the Br(-)/Br(3)(-) redox couple. For the dyes for which the HOMO levels are more positive than the redox potential of Br(-)/Br(3)(-) sufficient driving forces lead to the longer effective electron-diffusion lengths and almost the same efficient dye regenerations, whereas for the dyes for which the HOMO levels are similar to the redox potential of Br(-)/Br(3)(-), insufficient driving forces lead to shorter effective electron-diffusion lengths and inefficient dye regenerations.     

Mononuclear Sb(V) Bromide Complexes with 3-Halopyridinium Cations: Synthesis,Structures, and Thermal Stability

Russian Journal of Coordination Chemistry - Mononuclear complexes (3-XPyH)[SbBr6] (X = Cl (I), Br (II)) are synthesized by the reactions of Sb2O3, Br2, and 3-XPy in HBr. Compound I is characterized...     

BiOX (X = Cl,Br, and I) Nanoplates Prepared by Surfactant-Free Microwave Synthesis and Their Photocatalytic Performance

Russian Journal of Physical Chemistry A - Bismuth oxyhalide (BiOX; X = Cl, Br, and I) nanoplates were successfully synthesized by microwave irradiation of surfactant-free aqueous solutions. X-rays...     

Highly Efficient Visible Light Plasmonic Photocatalyst Ag@Ag(Br,I)

The new plasmonic photocatalyst Ag@Ag(Br,I) was synthesized by the ion‐exchange process between the silver bromide and potassium iodide, then by reducing some Ag⁺ ions in the surface region of Ag(Br,I) particles to Ag⁰ species. Ag nanoparticles are formed from Ag(Br,I) by the light‐induced chemical reduction reaction. The Ag@Ag(Br,I) particles have irregular shapes with their sizes varying from 83 nm to 1 μm. The as‐grown plasmonic photocatalyst shows strong absorption in the visible light region because of the plasmon resonance of Ag nanoparticles. The ability of this compound to reduce Cr^VI under visible light was compared with those of other reference photocatalyst. The plasmonic photocatalyst is shown to be highly efficient under visible light. The stability of the photocatalyst was examined by X‐ray diffraction and X‐ray photoelectron spectroscopy. The XRD pattern and XPS spectra prove the stability of the plasmonic photocatalyst Ag@Ag(Br,I).     

Synthesis of water‐soluble cationic polymers with star‐like structure based on cyclodextrin core via ATRP

A range of novel cationic star‐like polymers (Star‐P(MeDMA)s) were synthesized through atom transfer radical polymerization (ATRP) by core‐first method, using a β‐cyclodextrin initiator with 21 initiation sites (21Br‐β‐CD). Methyl chloride‐quaternized 2‐(dimethylamino)ethyl methacrylate (MeDMA) was polymerized in an aqueous medium using 21Br‐β‐CD, Cu(I)Br, and 2,2′‐dipyridyl as an initiator, catalyst, and ligand, respectively. The effects of polymerization temperature and monomer/initiator ratios on the degree and kinetics of polymerization were investigated. The molecular weights, hydrodynamic sizes, and charge densities of the quaternized polymers were characterized using gel permeation chromatography (GPC), dynamic light scattering (DLS), and colloidal titration, respectively. The results demonstrated that the moderate aqueous solubility of the 21Br‐β‐CD initiator had significant impact on the physicochemical properties of the obtained star polymers. The polymerization of 500/1/2/5 ([M]₀/[I]₀/[Cu(I)₀/[L]₀]) at 90 °C for 6 h was found to be the best condition to synthesize the proposed cationic star polymer with well‐defined structures in aqueous medium. The nonlinear relationship between the apparent charge density and the particle size of the cationic star polymers was further revealed by GPC and DLS measurements. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 6345–6354, 2005     

(Ph)3PBr][Br7], [(Bz)(Ph)3P]2[Br8], [(n-Bu)3MeN]2[Br20], [C4MPyr]2[Br20], and [(Ph)3PCl]2[Cl2I14]: extending the horizon of polyhalides via synthesis in ionic liquids

The five polyhalides [(Ph)(3)PBr][Br(7)], [(Bz)(Ph)(3)P](2)[Br(8)], [(n-Bu)(3)MeN](2)[Br(20)], [C(4)MPyr](2)[Br(20)] ([C(4)MPyr] = N-butyl-N-methylpyrrolidinium), and [(Ph)(3)PCl](2)[Cl(2)I(14)] were prepared by the reaction of dibromine and iodine monochloride in ionic liquids. The compounds [(Ph)(3)PBr][Br(7)] and [(Bz)(Ph)(3)P](2)[Br(8)] contain discrete pyramidal [Br(7)](-) and Z-shaped [Br(8)](2-) polybromide anions. [(n-Bu)(3)MeN](2)[Br(20)] and [C(4)MPyr](2)[Br(20)] exhibit new infinite two- and three-dimensional polybromide networks and contain the highest percentage of dibromine ever observed in a compound. [(Ph)(3)PCl](2)[Cl(2)I(14)] also consists of a three-dimensional network and is the first example of an infinite polyiodine chloride. All compounds were obtained from ionic liquids as the solvent that, on the one hand, guarantees for a high stability against strongly oxidizing Br(2) and ICl and that, on the other hand, reduces the high volatility of the molecular halogens.     

Synthesis,characterization, crystal structures and antibacterial activities of some Schiff bases with N<Subscript>2</Subscript>O<Subscript>2</Subscript> donor sets

A series of Schiff base compounds were synthesized by the reaction of different 3,5-dihalosalicylaldehyde (halo atoms equal to Cl, Br and I) with polymethylenediamines of varying chain length. The Schiff bases were characterized using FT-IR, UV–Vis, ¹H NMR, ¹³C NMR and mass spectroscopic techniques, and elemental analyses (CHN), and crystal structure of some compounds was determined by X-ray crystallography. The in vitro biological screening effects of the synthesized compounds were tested against different microbial kinds. The results revealed that all compounds were biologically active.