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Quasi-2D Heisenberg Antiferromagnets [CuX(pyz)2](BF4) with X = Cl and Br
Two Cu2+ coordination polymers [CuCl(pyz)2](BF4) 1 and [CuBr(pyz)2](BF4) 2 (pyz = pyrazine) were synthesized in the family of quasi two-dimensional (2D) [Cu(pyz)2]2+ magnetic networks. The layer connectivity by monatomic halide ligands results in significantly shorter interlayer distances. Structures were determined by single-crystal X-ray diffraction. Temperature-dependent X-ray diffraction of 1 revealed rigid [Cu(pyz)2]2+ layers that do not expand between 5 K and room temperature, whereas the expansion along the c-axis amounts to 2%. The magnetic susceptibility of 1 and 2 shows a broad maximum at ～8 K, indicating antiferromagnetic interactions within the [Cu(pyz)2]2+ layers. 2D Heisenberg model fits result in J∥ = 9.4(1) K for 1 and 8.9(1) K for 2. The interlayer coupling is much weaker with |J⊥| = 0.31(6) K for 1 and 0.52(9) K for 2. The electron density, experimentally determined and calculated by density functional theory, confirms the location of the singly occupied orbital (the magnetic orbital) in the tetragonal plane. The analysis of the spin density reveals a mainly σ-type exchange through pyrazine. Kinks in the magnetic susceptibility indicate the onset of long-range three-dimensional magnetic order below 4 K. The magnetic structures were determined by neutron diffraction. Magnetic Bragg peaks occur below TN = 3.9(1) K for 1 and 3.8(1) K for 2. The magnetic unit cell is doubled along the c-axis (k = 0, 0, 0.5). The ordered magnetic moments are located in the tetragonal plane and amount to 0.76(8) μB/Cu2+ for 1 and 0.6(1) μB/Cu2+ for 2 at 1.5 K. The moments are coupled antiferromagnetically both in the ab plane and along the c-axis. The Cu2+ g-tensor was determined from electron spin resonance spectra as gx = 2.060(1), gz = 2.275(1) for 1 and gx = 2.057(1), gz = 2.272(1) for 2 at room temperature.
Kubus, Mariusz,Lanza, Arianna,Scatena, Rebecca,Dos Santos, Leonardo H. R.,Wehinger, Bj?rn,Casati, Nicola,Fiolka, Christoph,Keller, Lukas,Macchi, Piero,Rüegg, Christian,Kr?mer, Karl W.
p. 4934 - 4943
(2018)
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GALVANOSTATIC PULSE PLATING OF COPPER AND COPPER (I) HALIDES FROM ACID COPPER (II) HALIDE SOLUTIONS.
CuX (X equals Cl or Br) is formed during the galvanostatic pulse plating of copper from acid solutions containing Cu**2** plus and X** minus . The reaction Cu**2** plus plus Cu degree plus 2X** minus yields 2CuX occurs in the relaxation period of the puls
Yeow,Hibbert
p. 786 - 790
(1983)
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Beyond Classical Coordination Chemistry: The First Case of a Triply Bridging Phosphine Ligand
The first example of a triply bridging (μ3-P) phosphine ligand has been discovered in the crown-shaped [Cu3(μ2-Hal)3L] (Hal=Cl, Br, or I) complexes supported by tris[2-(2-pyridyl)ethyl]phosphine (L). Theoretical analysis completely confirms the observed μ3-P-bridging pattern, revealing the interaction of the same lone pair of phosphorus with three valence 4s-orbitals of Cu atoms. The presented complexes exhibit outstanding blue phosphorescence (λem=442–465 nm) with the quantum efficiency reaching 100 %. The complex [Cu3(μ2-I)3L] also exhibits remarkable thermo- and mechanochromic luminescence resulting in a sharp change in the emission colour upon external stimuli. These findings essentially contribute to coordination chemistry of the pnictine ligands.
Baranov, Andrey Y.,Pritchina, Elena A.,Berezin, Alexey S.,Samsonenko, Denis G.,Fedin, Vladimir P.,Belogorlova, Nataliya A.,Gritsan, Nina P.,Artem'ev, Alexander V.
p. 12577 - 12584
(2021)
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Synthesis, crystal structure and properties of CuBr(2,3-dimethylpyrazine) coordination polymers
Reaction of CuBr with an excess of 2,3-dimethylpyrazine in acetonitrile leads to the formation of the literature known ligand-rich 1:1 compound poly[μ2-bromo-μ2-2,3-dimethylpyrazine-N, N′-copper(I)] (1). On heating this compound in a thermobalance a transformation into the new ligand-deficient 2 :1 compound poly[di- μ3-bromo-μ2-2,3-dimethylpyrazine-N, N′-dicopper(I)] (3) is observed, which later was also prepared in solution. This compound crystallizes in the monoclinic space group P2 1/n with all atoms in general positions. In the crystal structure the Cu atoms are surrounded by three Br atoms and one 2,3-dimethylpyrazine ligand within a distorted tetrahedron. The tetrahedra are connected via common Br edges into CuBr double chains, which are connected by the ligands into layers located in the ab plane. The formation of compounds 1 and 3 was also investigated in solution. The results have shown that compound 1 can only be prepared if an excess of the ligand is used. If CuBr and the ligand are reacted in a ratio of 1 : 1, in the beginning the literature known ligand-deficient 3 : 2 intermediate catena[tribromo-μ2-bis(μ2-2,3-dimethylpyrazine-N, N′)-tricopper(I)] (2) is obtained, which transforms within minutes into compound 3. If a crystalline suspension of compound 1 is stirred in acetonitrile a transformation into the most stable compound 3 is also observed. The luminescence properties of compounds 1 and 3 were investigated. The complexes show differences mainly in the emission spectra.
Je?, Inke,Taborsky, Petr,N?ther, Christian
p. 501 - 507
(2007)
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Electrical conductivity of CuSn5Br11 in solid and molten states
The electrical conductivity of solid and molten CuSn5Br11 and SnBr2 compounds was determined using classical a.c. bridge techniques and sealed capillary-type cells with platinum electrodes. The solid compound CuSn5Br11 may be a fast Cu+ ion conductor. The specific conductance of the molten compound is nearly the same as that of the molten stannous bromide. Its conduction is mostly due to motion of the anions.
Wojakowska,Kundys
p. 3780 - 3784
(1990)
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A thermoanalytical study of copper(I) thiocarbamide compounds
Hydrated isostructural 1:3 complexes of copper(I) chloride and bromide with thiourea were synthesised and their thermal decomposition studied by simultaneous TG/DTA complemented by ex situ FTIR and XRD studies. The decomposition of Cu(tu)3Cl·H2O is initiated by dehydration around 100°C, followed by a total multi-step degradation of the structure in the temperature range of 200-600°C. The counter ion has some influence on the temperatures and composition of the solid residue. The results were compared with those obtained with the 1:1 complex Cu(tu)Cl 1/2H2O.
Krunks,Leskelae,Mutikainen,Niinistoe
p. 479 - 484
(1999)
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New Cu(i) halide complexes showing TADF combined with room temperature phosphorescence: The balance tuned by halogens
A series of Cu(i) halide complexes derived from tris(2-pyridyl)phosphine (Py3P), [Cu2(Py3P)2X2] (X = Cl, Br, I), have been synthesized by a straightforward reaction in solution or through a mechanochemical route. At room temperature, the solid complexes exhibit bright dual-mode photoluminescence (λmax = 520-550 nm, τ = 14.5-20.0 μs, and ΦPL ≈ 53%), expressed by thermally activated delayed fluorescence (TADF) combined with phosphorescence (PH), originating from 1(M + X)LCT and 3(M + X)LCT excited states, respectively. Remarkably, the balance of these radiative processes at 300 K is regulated by halogen atom nature, switching from TADF-assisted phosphorescence to PH-admixed TADF. The emission of [Cu2(Py3P)2Cl2] at 300 K is largely contributed by PH (73%) admixed with the TADF fraction (27%) and [Cu2(Py3P)2Br2] also emits mainly PH (65%) admixed with the larger TADF fraction (35%). Meanwhile, for [Cu2(Py3P)2I2], the TADF channel becomes dominating (61%) and PH contribution drops to 39%. The photophysical study corroborated by (TD)DFT computations has revealed that this effect arises mainly from the narrowing of the ΔE(S1 - T1) gap of the [Cu2(Py3P)2X2] complexes in the order Cl (1500 cm-1) > Br (1250 cm-1) > I (1000 cm-1) which facilitates the TADF pathway and suppresses PH in the same order.
Artem'Ev, Alexander V.,Baranov, Andrey Yu.,Berezin, Alexey S.,Kolesnikov, Ilya E.,Mazur, Anton S.,Plyusnin, Viktor F.,Samsonenko, Denis G.,Tolstoy, Peter M.
p. 3155 - 3163
(2020)
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Two enantiomers of [Cu3(mnt)3]3- as ligands to Cu(i) or Ag(i) in building [Cu6M2(mnt) 6]4- complexes (M = Cu or Ag) with the reversal of the reaction by X- (X = Cl, Br)
Two enantiomers of [Bu4N]3[Cu3(mnt) 3] (1) formed by Na2(mnt) (mnt = maleonitriledithiolate, [S2C2(CN)2]2-) and CuCl in a 11 molar ratio react further with MCl (M = Cu or Ag) involving both the enantiomers of 1 to produce the larger complex, [Bu4N]4[Cu 6M2(mnt)6] (M = Cu (2), Ag (3)) from which the capped Cu+ or Ag+ ion can readily be removed by Bu 4NX (X = Cl, Br), reverting 2 or 3 back to 1. Such reversal does not work with non-coordinating anions like BF4-, ClO 4- and PF6-. The Royal Society of Chemistry.
Maiti, Biplab K.,Pal, Kuntal,Sarkar, Sabyasachi
p. 1003 - 1008
(2008)
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On the oximine complexes of transition metals. 106. Spectroscopic and DSC study of some complexes of the types [Cu(DioxH)2] and [CuX2·DioxH2]
Several new complexes of the types [Cu(DioxH)2] and [CuX2·DioxH2] (DioxH2: aliphatic or alicyclic α-dioxime) were obtained and characterized by means of near and far Fourier transformation IR spectroscopy. The t
Zsako,Nagy,Varhelyi,Novak,Lovasz
p. 421 - 429
(1998)
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Crystal Structure of High Temperature Phase and Ionic Conductivity Mechanism of CuHgSX (X = Cl, Br)
We found a new ionic conduction phase in CuHgSCl above 373 K and in CuHgSBr above 346 K. The crystal structures of these novel phases have been determined by Rietveld refinement of powder X-ray diffraction patterns. The electric conductivity at 500 K measured by AC impedance method was 1.4 × 10-5 S cm-1 for CuHgSCl and 4.0 × 10-6 S cm-1 for CuHgSBr. The activation enthalpy was determined to be 53 kJ mol-1 for CuHgSCl and 67 kJ mol-1 for CuHgSBr. The ionic transport number measurements indicated that Cu+ ions constitute the majority charge carriers in these samples. The electronic contribution to the conduction process is small in comparison with the Cu+ ionic contribution. The charge density analysis by the maximum entropy method (MEM) combined with Rietveld analysis clearly showed that the Cu+ ionic conduction path was along the crystallographic (100) direction.
Moro'oka, Masakazu,Ohki, Hiroshi,Yamada, Koji,Okuda, Tsutomu
p. 2111 - 2115
(2003)
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A Comparative Study of the Kinetics and Mechanism of Reactions between Copper(I) Iodide and Mercury(II) Halides in Solid State
Kinetics and mechanisms of reactions of HgI2, HgBrI, or HgBr2 with CuI were studied in the solid state.Mercury(II) halides react via vapor phase, and reactions proceed through counter diffusion of Cu+ and Hg2+.X-Ray and chemical analyses indicate that powdered CuI gives Cu2HgI4 when mixed with HgI2 and a mixture of Cu2HgI4 and CuBr when mixed with HgJBrI.CuI and HgBr2 react differently in different molar ratios.In a 1:2 molar ratio mixture of CuI and HgBr2, a new product CuHgBr3 and HgBrI are obtained.Data for lateral diffusion best fit the equation Xn=kt where X is the thickness of product layer at time t, and n and k are const.Formation of solid solutions among reactant and product phases is also noted.
Beg, Mirza Aijaz,Ahmad, Afaq
p. 3607 - 3611
(1982)
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Synthesis and characterizations of nanoribbons and monodispersed nanocrystals of CuBr
Nanoribbons and monodispersed nanocrystals of CuBr have been prepared by a simple reaction between CuO suspension, NH2OH·HCl and KBr in the presence of deionized gelatin at 10°C. The products were characterized by X-ray powder diffraction, transmission electron microscopy and UV-vis absorption spectroscopy. The sizes of the monodispersed nanocrystals of CuBr were estimated by Debye-Scherrer formula according to XRD spectrum.
Yang, Ming,Zhu, Jun-Jie
p. 265 - 270
(2005)
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Tris(chalcogenato)carbenium
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Ohlmann, Dietmar
p. 300 - 303
(1996)
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Two modifications of copper(I) Octahedro-hexatungsten(II) tetradecabromide, Cu2[W6Br14]
The reaction of W6Br12 with CuBr sealed in an evacuated silica tube at the temperature gradient 925/915 K and annealing at 625/300 K yields a mixture of orthorhombic α-Cu2[W6Br14] and cubic β-Cu2[W6Br14] in the low temperature zone. α-Cu2[W6Br14] crystallizes in the space group Pbca (no. 61), a = 15.126 A, b = 9.887 A, c = 15.954 A, Z = 4, oP88, and β-Cu2[W6Br14] crystallizes in the space group Pn3 (no. 201), a = 13.391 A, Z = 4, cP88. The crystal structures are built up by [(W6Bri8)Bra6] 2- cluster anions and Cu+ cations. The cluster anions show only in the peripheral shells small deviation from m3m symmetry (d(W-W) = 2.630 A; d(W-Bri) = 2.618 A; d(W-Bra) = 2.614 A). The anions are arranged in a slightly compressed bcc pattern (α) and ccp (β) pattern, respectively. The Cu+ cations are trigonal-planar coordinated by Bra ligands with d(Cu-Br) = 2.377 A (α) and 2.378 A (β). The cubic β-modification is diamagnetic with an unexpected large susceptibility (Xmol = -884×10-6 cm3 mol-1) and have a band gap of 2.8 eV. It decomposes under dynamic vacuum in two steps at 795 K und 1040 K.
Zheng, Yue-Qing,Grin, Yuri,Peters, Karl,Von Schnering, Hans Georg
p. 959 - 964
(1998)
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Two anionic [CuI6X7]nn- (X=Br and I) chain-based organic-inorganic hybrid solids with N-substituted benzotriazole ligands
Solvothermal reactions of the flexible ligand 1,6-Bi(benzotriazole)hexane with CuI and KI or CuBr and KBr in ethanol generate two hybrid compounds, namely, {(HETA)[(Cu6I7)(ETA)2]}n(1) and {K(Cu6Br7)(BBTH)}n(2) (ETA=N-ethylbenzotriazole, HETA=protonated N-ethylbenzotriazole, BBTH=1,6-bi(benzotriazole)hexane). In 1, two [Cu3I4] vertex missing cubane-like subunits link each other by sharing one I atom to give a [Cu6I7] cluster, which further form novel 1D [Cu6I7]nn- anionic chain. Two in-situ generated ETA ligands finished the 4-coordinated environments of copper centers and another one discrete protonated ETA ligand keeps the charge neutrality for 1. In complex 2, bowl-shaped [Cu5Br4] clusters and rhomboid [Cu2Br2] dimers link each other to generate a [Cu6Br7]nn- 1D chain. BBTH ligands complete the tetrahedral spheres of Cu(I), and 7-coordinated K atoms further extend the 1D chain motifs to a 2D hybrid layer of 2. The UV-vis diffuse reflectance spectrum and luminescence measurements show that compound 1 and 2 both are potential semiconductor and photoluminescence materials.
Gao, Xia,Zhai, Quan-Guo,Li, Shu-Ni,Xia, Rui,Xiang, Hai-Juan,Jiang, Yu-Cheng,Hu, Man-Cheng
p. 1150 - 1158
(2010)
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Growth and characterization of highly oriented CuBr thin films through room temperature electrochemical route
A simple electrochemical process has been demonstrated to grow highly oriented copper(I) bromide thin films on indium-doped tin oxide (ITO) glass through reducing CuBr2 in aqueous solutions at room temperature. The copper(I) bromide thin films grow preferential orientation along the 〈1 1 1〉 crystal axis from the X-ray diffraction patterns. The orientation growth of the CuBr thin films is little affected by the solution pH and applied potentials. The possible mechanism of the orientation growth has been discussed, and the surface energy of different crystal plane of CuBr crystal is believed to play an important role to control the orientation growth of the CuBr thin films. The oriented films exhibit intense free-exciton photoluminescence at room temperature.
Li, He,Liu, Run,Kang, Honglan,Zheng, Yifang,Xu, Zhude
p. 242 - 246
(2008)
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Synthesis, Thermal Properties and Crystal Structure of Twinned Crystals of the New Coordination Polymer Poly[(CuBr)2(μ2- pyrimidine-N,N')]
Reaction of copper(I) bromide with pyrimidine in acetonitrile leads to the formation of crystals of the new coordination polymer poly[(CuBr) 2(μ2-pyrimidine-N,N')]. Indexing of the reflections yields a monoclinic primitive cell with a = 3.9119(2), b = 13.525(1), c = 15.346(1) A?, ?= 97.29(1)° and V = 805.4(1) A?3. Inspection of the reciprocal space shows weak reflections which might be indicative of a superstructure leading to a doubling of the crystallographic c-axis. The structure can be solved in space group P21/m but the refinement leads to very poor reliability factors (wR2 for all refl.: 62.57%, R1 for all Fo > 4σ(Fo) = 27.84%). A twin refinement assuming merohedral twinning drastically reduces the R-values (wR2 for all refl.: 7.27%, R1 for all Fo > 4σ(Fo) = 2.64%) and a structure model is obtained which consists of two crystallographically independent copper and bromine atoms and two pyrimidine ligands in the asymmetric unit. However, carefull inspection of this structure shows that the two crystallographically independent layers formed by the connection of the building blocks are very similar and that they are related by a translation by half of the crystallographic c-axis. As a result of that, the crystal is just a partial merohedral twin and the reflections which led to the assumption that the c-axis is twice as long are generated by the second twin domain. The structure was refined with the correct twin law (wR2 for all refl.: 6.70%, R1 for all Fo > 4σ(Fo) = 2.57%). By this procedure a reasonable structure model is obtained which consists of one crystallographically independent copper and bromine atom and one pyrimidine ligand. In the crystal structure CuBr double chains are formed which are connected into layers via μ-N,N' coordination by the N-donor ligands. On heating, the compound loses all of the ligands and transforms into CuBr within only one single step in an exothermic reaction.
N?ther, Christian,Je?, Inke,Bolte, Michael
p. 1105 - 1111
(2003)
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Molecular metals based on copper(II) 2,9,16,23-tetrahalo substituted phthalocyanine derivatives
Pure copper(II) 2,9,16,23-symmetrically tetrahalo substituted phthalocyanine complexes, CuPTX (where X = F, Cl, Br and I) were synthesized. Elemental analyses, electronic, IR, magnetic susceptibility measurements, ESR, X-ray diffraction and TGA studies were carried out on the above complexes both before and after iodine doping, to characterize and investigate the effect of substituents as well as the iodine doping on the electrical properties of the copper phthalocyanine complexes. Variations in the electrical conductivity of the complexes depend on the nature of the substituents and were found to show ～105 times improved electrical conductivity in comparison to the parent phthalocyanine. It is interesting to note that substitution and iodine doping showed remarkably increased electrical conductivity, nearly 1012 times the electrical conductivity of copper phthalocyanine. This may be due to a decrease in the metal-metal bond distance, increase in the approach of an ideal eclipsed system or due to the combined effects of both.
Achar,Jayasree
p. 719 - 733
(2000)
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Reactivity of thiazolidine-2-thione towards CuI/CuII: Synthesis and structures of [3-(2-thiazolin-2-yl)thiazolidine-2-thione]copper(I) bromide and [bis(2,2′-bipyridine)nitratocopper(II)] nitrate
Thiazolidine-2-thione (L1, NC3H5S2) reacted with copper(I) bromide in CH3CN under aerobic conditions and transformed through C-S bond cleavage into 3-(2-thiazolin-2-yl)thiazolidine-2-thione (L2, C3H4S2N-C3H4SN). This thio-ligand L2 with CuI ion yielded a three coordinate complex, [3-(2-Thiazolin-2-yl)thiazolidine-2-thione]copper(I)bromide 1a which crystallized in the triclinic system with the space group P1 as reported earlier. Treatment of 1a with bis(diphenylphosphino)methane (dppm) in dichloromethane also formed [3-(2-thiazolin-2-yl)thiazolidine-2-thione]copper(I) bromide 1b but it crystallized into the triclinic system with a new space group, P-1: 296(2) K, a, 7.3890(19); b, 8.473(2); c, 9.491(2) ?; α, 70.273(5); β, 67.170(5); γ, 84.949(5)°; R, 6.79%. Reactions of copper(II) nitrate with thiazolidine-2-thione followed by the addition of 2,2′-bipyridine or with 2,2′-bipyridine first followed by the addition of thiazolidine-2-thione, gave blue crystals in both the cases. The x-ray crystallography revealed stoichiometry of the complex formed as: [Cu(κ 2-N,N′-bipy)2(κ 1-ONO2)](NO3)2, which crystallized in monoclinic crystal system with space group, P21/n(14). Crystal data: 173(2) K, a, 11.318(1), b, 12.160(1), c, 14.967(1) ?; β = 98.01(1)°, R, 3.99%; 296(2) K, a, 11.340(5), b, 12.249(5), c, 15.065(6) ?; β = 98.04(2)°, R, 4.09%. [Figure not available: see fulltext.]
Lobana, Tarlok S.,Rani, Anu,Jassal, Amanpreet K.,Jasinski, Jerry P.
p. 149 - 153
(2015)
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Continuous and green microflow synthesis of azobenzene compounds catalyzed by consecutively prepared tetrahedron CuBr
An environmentally friendly and cross-selective process intensification for the continuous synthesis of symmetric aromatic azo compounds by using self-made cuprous bromide as the catalyst under mild conditions in the microreactor was developed. A novel tetrahedron cuprous bromide catalyst which shows outstanding catalytic activity and satisfactory stability has been synthesized in continuous flow microreactor. The online immobilization of self-made cuprous bromide on the catalyst bed achieved oxidative coupling of aromatic amines (oxygen as oxidant) and high-performance gas–liquid–solid three-phase reaction, which strongly limited the possibility of undesired reaction pathways, improving product selectivity and reducing waste generation. Meanwhile, the yield of azo-coupling reaction was up to 98% under optimized condition. As compared with earlier traditional method (diazotization reaction) for synthesizing azobenzene, the designed micro-flow process displays signi?cant advances in terms of selectivity, waste emissions, sustainability and productivity. The combination of online immobilization of self-made cuprous bromide and precise and safe control through the microreactor provides a green solution for the industrial production of valuable aromatic azo compounds.
Qin, Hong,Liu, Chengkou,Lv, Niuniu,He, Wei,Meng, Jingjing,Fang, Zheng,Guo, Kai
(2019/12/24)

Total Synthesis of Marine Alkaloid Hyellazole and its Derivatives
The total synthesis of the naturally occurring marine alkaloids hyellazole and chlorohyellazole was attempted from the corresponding easily accessible 2-methyl-1-ketotetrahydrocarbazoles obtained through the Japp–Klingemann reaction, followed by Fischer indole cyclization and subsequent Grignard coupling with phenylmagnesium bromide. Grignard coupling with 2-methyl-1-ketotetrahydrocarbazole unfortunately led directly to 2-methyl-1-phenylcarbazole through dehydration followed by aromatization through aerial oxidation, but application of the same reaction conditions to 6-chloro-2-methyl-2,3,4,9-tetrahydro-1H-carbazol-1-one, with careful treatment, led to the isolation of 6-chloro-2-methyl-1-phenyl-4,9-dihydro-3H-carbazole. However, selenium dioxide oxidation of this dihydrochloro derivative led to the formation of 6-chloro-2-methyl-1-phenyl-9H-carbazole. A different route was then adopted: a suitably substituted aromatic amine was used to establish the substitution pattern of the required carbazole derivative with a bromo group at C-1, and the required phenyl group at the 1-postion was then attached through Suzuki–Miyaura cross-coupling to furnish hyellazole.
Chakraborty, Suchandra,Saha, Chandan
p. 2013 - 2021
(2018/05/15)

Synthesis, structures and antimicrobial activity of copper derivatives of N -substituted imidazolidine-2-thiones: Unusual bio-activity against Staphylococcus epidermidis and Enterococcus faecalis
The main objective of this study was to explore the antimicrobial activity of several copper(i) complexes with N,S-donor thio-ligands against Gram positive bacteria, namely Staphylococcus aureus (MTCC 740), Staphylococcus epidermidis (MTCC 435), and Enter
Lobana, Tarlok S.,Aulakh, Jaspreet K.,Sood, Heena,Arora, Daljit S.,Garcia-Santos, Isabel,Kaur, Manpreet,Duff, Courtney E.,Jasinski, Jerry P.
p. 9886 - 9900
(2018/06/18)

Sulfones as Synthetic Linchpins: Transition-Metal-Free sp3–sp2 and sp2–sp2 Cross-Couplings Between Geminal Bis(sulfones) and Organolithium Compounds
A valuable umpolung strategy that highlights the ambiphilic nature of the bis(phenylsulfonyl)methyl synthon and demonstrates its utility as a synthetic linchpin is reported. Although the bis(phenylsulfonyl)methyl group is typically introduced as an sp3-carbon nucleophile, it is demonstrated that it can also function as an effective sp2-carbon electrophile in the presence of organolithium nucleophiles. Alkyl- and aryllithiums couple with the central carbon of the bis(phenylsulfonyl)methyl unit to ultimately generate trisubstituted alkenes, comprising formal sp3–sp2 and sp2–sp2 cross-couplings between organolithium reagents and bis(sulfones). This process occurs almost instantaneously at ?78 °C in the absence of any transition metals. By developing this curious transformation, it has been demonstrated that bis(phenylsulfonyl)methane is a valuable synthetic linchpin, which can undergo two C?C bond-forming processes as an sp3-nucleophile, followed by a third C?C bond-forming reaction as an effective sp2-electrophile. This discovery significantly enhances the utility of this ubiquitous, but underutilized, linker group.
Trost, Barry M.,Kalnmals, Christopher A.
supporting information
p. 9066 - 9074
(2018/06/29)

Synthesis, structures, antimicrobial activity and biosafety evaluation of pyridine-2-formaldehyde-N-susbtituted-thiosemicarbazonates of copper(ii)
Pyridine-2-formaldehyde-N1-substituted-thiosemicarbazones {(C5H4N4)HC2═N3-N2(H)-C1═(S)N1HR} (abbrev. HL1-R: R = Me, Et, Ph) with copper(i) halides in an acetonitrile-dichloromethane mixture (1?:?1, v/v) have yielded a novel series of CuII complexes with a central coordination core: [CuIIX(N,N,S-L1-R)] (R = Me, Et, Ph: X = I, 1-3; Br, 4-6, Cl, 7-9), which have been characterized with the help of analytical data, IR, UV-visible and ESR spectroscopy, ESI-mass spectrometry and single crystal X-ray crystallography. The thio-ligands coordinate to CuII as anions (L1-R)? through pyridyl nitrogen-N4, azomethine nitrogen-N3 and thiolato sulfur and CuII is further bonded to iodide, bromide or chloride. In order to explore their bio-activity, complexes (1-9) as well as the previously reported CuII complexes of 2-benzoylpyridine-N-substituted thiosemicarbazones {(C5H4N4)(C6H5)-C2═N3-N2(H)-C1═(S)-N1HR; HL2-R}, namely, [CuIIX(N,N,S-L2-R)] (R = Me, Et, Ph: X = I, 10-12; Br, 13-15; Cl, 16-18), have been evaluated for their antimicrobial potential against different microbial strains. The microbial strains investigated are Staphylococcus aureus (MTCC740), Klebsiella pneumoniae (MTCC530), Shigella flexneri (MTCC1457), Salmonella typhimurium 1 (MTCC98), Salmonella typhimurium 2 (MTCC1251), Escherichia coli (MTCC119), Staphylococcus epidermidis (MTCC435), methicillin resistant Staphylococcus aureus (MRSA) and a yeast culture Candida albicans (MTCC227). Several complexes tested have shown high antimicrobial activity; specifically, against methicillin resistant Staphylococcus aureus, Staphylococcus epidermidis and Salmonella typhimurium 2; the activity is found to be high at low minimum inhibitory concentration (MIC) values as compared to that of the standard Gentamicin. Using MTT cytotoxicity assay {MTT = 3-[(4,5-dimethylthiazol-2-yl)-2,5-diphenyl]tetrazolium bromide}, complexes tested were found to be biosafe with high cell viability (90-98%).
Kaushal, Mani,Lobana, Tarlok S.,Nim, Lovedeep,Kaur, Jaskamal,Bala, Ritu,Hundal, Geeta,Arora, Daljit S.,Garcia-Santos, Isabel,Duff, Courtney E.,Jasinski, Jerry P.
p. 15879 - 15894
(2018/10/04)

X-ray Absorption and Electron Paramagnetic Resonance Guided Discovery of the Cu-Catalyzed Synthesis of Multiaryl-Substituted Furans from Aryl Styrene and Ketones Using DMSO as the Oxidant
The first example of DMSO serving not only as a solvent but also as an oxidant to promote the oxidation of Cu(I) to Cu(II) has been demonstrated. X-ray absorption and electron paramagnetic resonance evidence revealed a single-electron redox process where DMSO could oxidize Cu(I) to Cu(II). The novel discovery guided the rational design of copper-catalyzed oxidative cyclization of aryl ketones with styrenes to furans, providing a new method for the synthesis of multiaryl-substituted furans from cheap and readily available starting materials.
Wu, Yong,Huang, Zhiyuan,Luo, Yi,Liu, Dong,Deng, Yi,Yi, Hong,Lee, Jyh-Fu,Pao, Chih-Wen,Chen, Jeng-Lung,Lei, Aiwen
supporting information
p. 2330 - 2333
(2017/05/12)

Synthesis and crystal structure of [chlorobis(triphenylphospino)(p-chlorobenzaldehyde thiosemicarbazone)] copper(I) complex
Reactions of copper(I) halides with p-chlorobenzaldehyde thiosemicarbazone (H1L) and triphenylphosphine in 1: 1: 2 molar ratio yielded complexes of stoichiometry, [CuX(η 1-S- H 1L)(Ph3P)2] (X = I, 1: Br, 2; Cl, 3). All the three complexes were characterized using analytical (CHNS) and spectroscopic (IR, 1H NMR) techniques. The structure of complex 3 was confirmed by X-ray crystallography. It has been found to crystallize in the triclinic system with space group P-1 and unit cell parameters: a = 10.207(5) ?, b = 13.027(5) ?, c = 16.269(5) ?, α= 100.054(5), β= 99.228(5) and γ= 97.234(5). This complex has distorted tetrahedral geometry with two phosphorus atoms from two triphenylphosphine ligands, thione sulfur of thiosemicarbazone ligand and chloride ion occupying the four corners of the tetrahedron. The structure of complex 3 was in contrast to sulfur-bridged dinuclear complex of copper(I) chloride with benzaldehydethiosemicarbazone, [Cu2Cl2(μ 2-S-Hbtsc)2(Ph3P)2] 2H2O. The intermolecular H-bonding, Cl ?HC ph, 2.733 ? and π interactions, {CHph?π, 2.796; 2.776 ?} in this complex led to the formation of 1D chain. Two such 1D chains were cross-linked via, Cl ?HC ph, 2.896 ? H-bonding to form a 2D network. [Figure not available: see fulltext.]
Khan, Ashiq,Sharma, Poonam,Rajnikant,Gupta, Vivek K.,Padha, Naresh,Sharma, Rekha
p. 185 - 191
(2016/02/18)

Synthesis, Spectroscopy, and Structures of Mono- and Dinuclear Copper(I) Halide Complexes with 1,3-Imidazolidine-2-thiones
Copper(I) halides with triphenyl phosphine and imidaozlidine-2-thiones (L-NMe, L-NEt, and L-NPh) in acetonitrile/methanol (or dichloromethane) yielded copper(I) mixed-ligand complexes: mononuclear, namely, [CuCl(κ1-S-L-NMe)(PPh3)2] (1), [CuBr(κ1-S-L-NMe)(PPh3)2] (2), [CuBr(κ1-S-L-NEt)(PPh3)2] (5), [CuI(κ1-S-L-NEt)(PPh3)2] (6), [CuCl(κ1-S-L-NPh)(PPh3)2] (7), and [CuBr(κ1-S-L-NPh)(PPh3)2] (8), and dinuclear, [Cu2(κ1-I)2(μ-S-L-NMe)2(PPh3)2] (3) and [Cu2(μ-Cl)2(κ1-S-L-NEt)2(PPh3)2] (4). All complexes were characterized with analytical data, IR and NMR spectroscopy, and X-ray crystallography. Complexes 2-4, 7, and 8 each formed crystals in the triclinic system with Pβar{1}$ space group, whereas complexes 1, 5, and 6 crystallized in the monoclinic crystal system with space groups P21/c, C2/c, and P21/n, respectively. Complex 2 has shown two independent molecules, [(CuBr(κ1-S-L-NMe)(PPh3)2] and [CuBr(PPh3)2] in the unit cell. For X = Cl, the thio-ligand bonded to metal as terminal in complex 4, whereas for X = I it is sulfur-bridged in complex 3.
Walia, Simran,Kaur, Supreet,Kaur, Jaspreet,Sandhu, Amanpreet K.,Lobana, Tarlok S.,Hundal, Geeta,Jasinski, Jerry P.
p. 1728 - 1736
(2015/08/18)

Synthesis, molecular structures and ESI-mass studies of copper(I) complexes with ligands incorporating N, S and P donor atoms
Equimolar reaction of copper(I) bromide with 2-thiouracil (tucH2) in acetonitrile-methanol formed a light yellow solid which on subsequent treatment with a mole of triphenyl phosphine (PPh3) in chloroform has yielded a sulfur-bridged dinuclear complex, [Cu2Br2(μ-S-tucH2)2(PPh3)2] 2CHCl3 1. A reaction of copper(I) bromide with two moles of 2,4-dithiouracil (dtucH2) in acetonitrile-methanol followed by addition of two moles of PPh3, designed to form [Cu(μ-S,S-dtuc)2(PPh3)4Cu] 2a, instead resulted in the formation of previously reported polymer, {CuBr(μ-S,S-dtucH2)(PPh3)}n 2. Reaction of copper(I) iodide with 2-thiouracil (tucH2) and PPh3 in 1:1:2 molar ratio (Cu:H2tuc:PPh3) as well as that of copper(I) thiocyanate with pyridine-2-thione (pySH) or pyrimidine-2-thione (pymSH) and PPh3 in similar ratio, yielded an iodo-bridged unsymmetrical dimer, [(PPh3)2(μ-I)2Cu(PPh3)] 3 and thiocyanate bridged symmetrical dimer, [(PPh3)2Cu(μ-N,S- SCN)2Cu(PPh3)2] 4, respectively. In both the latter reactions, thio-ligands which initially bind to Cu metal center, are de-ligated by PPh3 ligand. Crystal data: 1, P21/c: 173(2) K, monoclinic, a, 13.4900(6); b, 17.1639(5); c, 12.1860(5) ?; β, 111.807(5) a; R, 5.10%; 2, Pbca: 296(2) K, orthorhombic, a, 10.859(3); b, 17.718(4); c, 23.713(6) ?; α=β=γ, 90 a; R, 4.60%; 3, P21: 173(2) K, monoclinic, a, 10.4208(7); b, 20.6402(12); c, 11.7260(7) ?; β, 105.601(7)a; R, 3.97%; 4, P-1: 173(2) K, triclinic, a, 10.2035(4); b, 13.0192(5); c, 13.3586(6) ?; α, 114.856(4); β, 92.872(4)a; γ, 100.720(4)a; R, 3.71%. ESI-mass studies reveal different fragments of complexes.
Lobana, Tarlok S.,Kaur, Arvinder,Sharma, Rohit,Bala, Madhu,Jassal, Amanpreet K.,Duff, Courtney E.,Jasinski, Jerry P.
p. 1859 - 1869
(2015/12/11)

DINAPHTHOTHIOPHENE COMPOUND, COMPOSITION FOR ORGANIC THIN FILM TRANSISTOR INCLUDING THE DINAPHTHOTHIOPHENE AND ORGANIC THIN FILM TRANSISTOR USING THE SAME
PROBLEM TO BE SOLVED: To provide a dinaphthothiophene compound capable of producing an organic thin film transistor operating at a high mobility. SOLUTION: Provided is a dinaphthothiophene compound represented by formula (A), in which at least one among R1 to R12 denotes a substitutional group represented by formula (1); and Y denotes a 4 to 30C substituted or unsubstituted alkyl group. COPYRIGHT: (C)2015,JPO&INPIT
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Paragraph 0092; 0095

(2018/10/31)

Coordination variability of CuI in multidonor heterocyclic thioamides: Synthesis, crystal structures, luminescent properties and ESI-mass studies of complexes
The chemistry of copper(i) with scarcely investigated heterocyclic thioamides, particularly 2,4,6-trimercaptotriazine, purine-6-thione, 2,4-dithiouracil, 2-thiouracil and pyrimidine-2-thione is described. The interaction of 2,4,6-trimercaptotriazine (tmtH3) with [Cu(CH 3COO)(PPh3)2] resulted in a pair of bond isomers: [Cu(κ1N-tmtH2)(PPh3) 2] (6a), [Cu(κ1N,κ1S-tmtH 2)(PPh3)2] (6b); with copper(i) bromide and PPh3, it formed a trinuclear complex, [Cu3Br 2(κ1N,κ1S, μ-S-tmtH 2)(PPh3)6] (7) with anionic tmtH 2-. The 2,4-dithiouracil with copper(i) halides (CuCl, CuBr) and PPh3 yielded dinuclear complexes: [Cu2(μ-Cl) (κ1S,κ1S-dtucH)(PPh3)4] (4) and [Cu2(μ-Br)(κ1S,κ1S- dtucH)(PPh3)4] (5) with unusual eight-membered metallacyclic rings. Pyrimidine-2-thione (pymSH) is an N,S-chelated anion in a mononuclear complex, [Cu(κ1N,κ1S-pymS) (PPh3)2] (1), whereas 2-thiouracil (tucH2) with copper(i) chloride and PPh3 yielded a tetrahedral complex, [CuCl(κ1S-tucH2)(PPh3)2] (3). Purine-6-thione (purSH2) coordinated to CuI in two different modes yielding mono- and di-nuclear complexes, [Cu(κ 1N,κ1S-purS)(PPh3)2] ·CH3OH (2a) and [Cu2(κ1N,μ-S- purS)2(PPh3)2] (2b). The existence of bond isomers (6a and 6b), synthesis of novel dinuclear (4 and 5) and rare trinuclear (7) complexes with unusual bonding patterns are the novel features of the present study. Complexes show intense emission bands in the 380-530 nm region with λem at 490 to 495 nm.
Lobana, Tarlok S.,Sandhu, Amanpreet K.,Sultana, Razia,Castineiras, Alfonso,Butcher, Ray J.,Jasinski, Jerry P.
p. 30511 - 30522
(2014/08/05)

1,2-asymmetric induction in diastereoselective zwitterionic aza-Claisen rearrangements: Key steps in optically active alkaloid synthesis
The zwitterionic aza-Claisen rearrangement of optically active N-allylpyrrolidines and α-phenoxyacetyl fluorides proceeds with complete simple diastereoselectivity (internal asymmetric induction) and complete 1,2-asymmetric induction to generate a new C-C bond adjacent to a chiral C-N-Boc functionality. The resulting γ,δ-unsaturated amides were cyclised to give the corresponding pyrrolizidinones, which enabled the determination of the relative configuration of the stereotriads. Vinyl group degradation and a final lactam reduction gave an optically active analogue of (+)-petasinine (a pyrrolizidine alkaloid). Furthermore, the stereotriad-containing amides should be useful key intermediates for the total synthesis of optically active elaeocarpin (an indolizidine alkaloid). Copyright
Heescher, Carolin,Schollmeyer, Dieter,Nubbemeyer, Udo
supporting information
p. 4399 - 4404
(2013/07/26)

Chemistry of heterocyclic 2-thiones: In situ generation of 3-(2-thiazolin-2-yl)thiazolidine-2-thione and 1,1′-dimethyl-2,2′- diimidazolyl sulfide and their coordination to CuI and Cu II
The chemical reactivity of copper(I) chloride/copper(I) bromide, [Cu I(NCCH3)4](BF4), and copper(II) nitrate towards a series of heterocyclic-2-thiones under aerobic conditions is described. Thiazolidine-2-thione (NC3H5S2) in CH3CN in the presence of copper(I) chloride/bromide and [Cu I(NCCH3)4](BF4) was transformed into 3-(2-thiazolin-2-yl)thiazolidine-2-thione (C3H4S 2N-C3H4SN) through C-S bond cleavage and the formation of a C-N bond between two heterocyclic rings. This new thio ligand (C3H4S2N-C3H4SN) chelates to CuI through N,S-donor atoms, and the third site is occupied by the halogen atoms (Cl, Br), which leads to the formation of three-coordinate CuI complexes, [CuIX(κ2-N,S-C 3H4S2N-C3H4SN)] [X = Cl (1), Br (2)], and a four-coordinate N,S-chelated complex, [Cu I(κ2-N,S-C3H4S 2N-C3H4SN)2](BF4) (3), is obtained in the presence of BF4-. In each case, the formation of CuSO4·5H2O was also observed. Upon reaction of 1-methylimidazoline-2-thione (N2C4H 6S) with [CuI(NCCH3)4](BF 4) or copper(II) nitrate in CH3CN or CH 3CN/MeOH, respectively, the thio ligand is converted into 1,1′-dimethyl-2,2′-diimidazolyl sulfide (N2C 4H5)2S (a thioether), which prefers to bind to CuII (in situ formed) to yield six-coordinate N,N-chelated octahedral complexes, namely, {CuII[κ2-N,N-(N 2C4H5)2S]2(κ 1-OH2)2}X2 [X = BF4 (6), NO3 (7)], with water in the axial positions. The transformation of the thio ligand into 1,1′-dimethyl-2,2′-diimidazolyl sulfide is also observed in its copper(I) chloride reaction in acetonitrile, which yields an N,N-chelated chloro-bridged dimer, {CuII2[κ 2-N,N-(N2C4H5)2S] 2(μ-Cl)2Cl2} (5). Reaction of copper(I) iodide with thiazolidine-2-thione and 1-methylimidazolidine-2-thione (N 2C4H8S) in acetonitrile yields an iodo-bridged dimer, [Cu2(κ1-S-NC3H5S 2)4(μ-I)2] (4), and a novel polymer, [Cu4(μ3-I)2(μ-I)2(μ-S- N2C4H8S)2(κ1-S- N2C4H8S)]n (8), respectively. Reactions of copper(I) halides (Cl, Br), [CuI(NCCH3) 4](BF4), and copper(II) nitrate with thiazolidine-2- thione, 1-methylimidazoline-2-thione, and imidazolidine-2-thione in different solvents result in C-S bond cleavage and the in situ production of sulfate. For example, thiazolidine-2-thione is transformed into a new thio ligand, 3-(2-thiazolin-2-yl)thiazolidine-2-thione, which forms compounds 1 and 2 depending on the anion. Copyright
Lobana, Tarlok S.,Sultana, Razia,Butcher, Ray J.,Castineiras, Alfonso,Akitsu, Takashiro,Fernandez, Francisco J.,Vega, M. Cristina
p. 5161 - 5170
(2013/10/22)

Microwave-assisted carbohydrohalogenation of first-row transition-metal oxides (M = V, Cr, Mn, Fe, Co, Ni, Cu) with the formation of element halides
The anhydrous forms of first-row transition-metal chlorides and bromides ranging from vanadium to copper were synthesized in a one-step reaction using the relatively inexpensive element oxides, carbon sources, and halogen halides as starting materials. The reactions were carried out in a microwave oven to give quantitative yields within short reaction times.
Berger, Matthias,Neumeyer, Felix,Auner, Norbert
supporting information
p. 11691 - 11693
(2013/11/19)

Thermal tuning of advanced Cu sol-gels for mixed oxidation state Cu/Cu xOy materials
In this report, we describe new conditions for the formation of copper gels and aerogels via epoxide addition to CuBr2 in dimethylformamide (DMF). These CuBr2-derived sols undergo a rapid gel transition and result in materials that have enhanced mechanical properties when compared with the gels derived from CuCl2. Additionally, upon air-annealing, they convert to nanoscopic CuO at temperatures much lower than the CuCl2 analogues. Moreover, annealing under nitrogen results in copper species with reduced oxidization states including Cu2O and metallic Cu. The ratio of copper oxidation states can be controlled by simple modification of the thermal program used to anneal the materials. The thermal reduction of the copper is attributed to retained DMF ligands in the as-prepared aerogels which was confirmed by FTIR spectroscopy. These aerogel materials were characterized by powder X-ray diffraction (PXRD), physisorption, thermogravimetric analysis (TGA), and temperature programmed reduction (TPR).
Baghi, Roya,Peterson, Geneva R.,Hope-Weeks, Louisa J.
p. 10898 - 10902
(2013/09/12)

Thermal tuning of advanced Cu sol-gels for mixed oxidation state Cu/Cu xOy materials
In this report, we describe new conditions for the formation of copper gels and aerogels via epoxide addition to CuBr2 in dimethylformamide (DMF). These CuBr2-derived sols undergo a rapid gel transition and result in materials that have enhanced mechanical properties when compared with the gels derived from CuCl2. Additionally, upon air-annealing, they convert to nanoscopic CuO at temperatures much lower than the CuCl2 analogues. Moreover, annealing under nitrogen results in copper species with reduced oxidization states including Cu2O and metallic Cu. The ratio of copper oxidation states can be controlled by simple modification of the thermal program used to anneal the materials. The thermal reduction of the copper is attributed to retained DMF ligands in the as-prepared aerogels which was confirmed by FTIR spectroscopy. These aerogel materials were characterized by powder X-ray diffraction (PXRD), physisorption, thermogravimetric analysis (TGA), and temperature programmed reduction (TPR).
Baghi, Roya,Peterson, Geneva R.,Hope-Weeks, Louisa J.
p. 10898 - 10902
(2013/09/23)

2-Benzoylpyridine thiosemicarbazone as a novel reagent for the single pot synthesis of dinuclear CuI-CuII complexes: Formation of stable copper(ii)-iodide bonds
2-Benzoylpyridine thiosemicarbazone {R1R2C 2N2·N3H-C1(S)-N 4H2, R1 = py-N1, R2 = Ph; Hbpytsc} with copper(i) iodide in acetonitrile-dichloromethane mixture has formed stable CuII-I bonds in a dark green CuII iodo-bridged dimer, [Cu2II(μ-I)2(η 3-N1,N2,S-bpytsc)2] 1. Copper(i) bromide also formed similar CuII-Br bonds in a dark green Cu II bromo-bridged dimer, [Cu2II(μ-Br) 2(η3-N1,N2,S-bpytsc) 2] 3. The formation of dimers 1 and 3 appears to be due to a proton coupled electron transfer (PCET) process wherein copper(i) loses an electron to form copper(ii), and this is accompanied by a loss of -N3H proton of Hbpytsc ligand resulting in the formation of anionic bpytsc-. When copper(i) iodide was reacted with triphenylphosphine (PPh3) in acetonitrile followed by the addition of 2-benzoylpyridine thiosemicarbazone in dichloromethane (Cu:PPh3:Hbpytsc in the molar ratio 1:1:1), both CuII dimer 1 and an orange CuI sulfur-bridged dimer, [Cu2II2(μ-S-Hbpytsc)2(PPh 3)2] 2 were formed. Copper(i) bromide with PPh3 and Hbpytsc also formed CuII dimer 3 and an orange CuI sulfur-bridged dimer, [Cu2IBr2(μ-S-Hbpytsc) 2(PPh3)2] 4. While complexes 2 and 4 exist as sulfur-bridged CuI dimers, 1 and 3 are halogen-bridged. The central Cu2S2 cores of 2 and 4 as well as Cu2X 2 of 1 (X = I) and 3 (X = Br) are parallelograms. One set of Cu II-I and CuII-Br bonds are short, while the second set is very long {1, Cu-I, 2.565(1), 3.313(1) A; 3, Cu-Br, 2.391(1), 3.111(1) A}. The Cu...Cu separations are long in all four complexes {1, 4.126(1); 2, 3.857(1); 3, 3.227(1); 4, 3.285(1) A}, more than twice the van der Waals radius of a Cu atom, 2.80 A. The pyridyl group appears to be necessary for stabilizing the CuII-I bond, as this group can accept π-electrons from the metal. The Royal Society of Chemistry 2012.
Lobana, Tarlok S.,Khanna, Sonia,Butcher, Ray J.
p. 4845 - 4851
(2012/06/04)

The influence of substituents (R) at N1 atom of furan-2-carbaldehyde thiosemicarbazones {(C4H3O)HC 2N3-N(H)-C1(S)N1HR} on bonding, nuclearity, H-bonded networks of copper(I) comp
The chemistry of copper(I) halides (CuX) with furan-2-carbaldehyde-N 1-substituted thiosemicarbazones {(C4H3O) HC2N3N2H-C1(S)N1HR, Hftsc-N1HR} in presence o
Lobana, Tarlok S.,Sharma, Rekha,Hundal, Geeta,Castineiras,Butcher, Ray Jay
p. 134 - 142
(2013/01/15)

Thiosemicarbazone derivatives of nickel and copper: The unprecedented coordination of furan ring in octahedral nickel(ii) and of triphenylphosphine in three-coordinate copper(i) complexes
The influence of substituents at the C2 carbon of N 1-substituted thiosemicarbazones, {C4H3X-C 2(CH3)N3-N2H-C1(S)N 1HR2} (X = O, S) on the geometry of nickel(ii) complexes has been investigated. The presence of a methyl group at the C2 position of 2-acetylfuran-N1-substituted thiosemicarbazones {(C 4H3O)-C2(CH3)N3-N 2H-C1(S)N1HR2, R2 = CH3, HaftscN-Me; C2H5, HaftscN-Et; C 6H5, HaftscN-Ph} induces unusual coordination by the furan ring and yielded high spin octahedral nickel(ii) complexes, [Ni(κ3-O, N3, S-aftscN-R2)2], CH31, C2H52, and 2[Ni((κ3-O, N3, S-aftscN-Ph)2] 3 (μeff = 2.98, 1; 2.96, 2; 2.92, 3). With 2-acetylthiophene-N1-substituted thiosemicarbazones, {(C4H3S)-C2(CH 3)N3-N2H-C1(S)N1HR 2, R2 = CH3, HattscN-Me; C2H 5, HattscN-Et; C6H5, HattscN-Ph}, N 3, S chelated low spin trans square planar complexes, {[Ni(κ3-O, N3, S-attscN-R2)2], R2 = CH3, 4; C2H5, 5; C 6H5, 6} with pendant thiophene rings have been obtained. The bigger sized sulfur atoms of the thiophene rings form short intramolecular contacts with the deprotonated hydrazinic nitrogen atoms (S...N 2) inhibiting its lability for possible coordination to nickel(ii). Complexes have one independent molecule (1) or two independent molecules (2, 3) in their respective crystal lattices. The simultaneous presence of methyl groups at the C2 and N1 atoms of 2-acetylthiophene-N 1-methylthiosemicarbazone (HattscN-Me) have facilitated the binding of triphenylphosphine in three-coordinate copper(i) halide complexes, [CuX(η1-S-HattscN-Me)(Ph3P)] (X, Br, 7; Cl, 8), which represent an unusual donor set of ligands, namely, triphenylphosphine, sulfur of a thio-ligand and a halide.
Singh Lobana, Tarlok,Kumari, Poonam,Sharma, Rekha,Castineiras, Alfonso,Butcher, Ray Jay,Akitsu, Takashiro,Aritake, Yoshikazu
p. 3219 - 3228
(2011/05/14)

Luminescence and thermal behavior by simultaneous TG/DTG-DTA coupled with MS of neutral copper (I) complexes with heterocyclic thiones
Copper(I) halide complexes formulated as [(L)CuX(μ2-L) 2CuX(L)] (X = Cl, Br and L = pyridine-2-thione (py2SH), or 4,6-dimethylpyrimidine-2-thione (dmpymtH)) were prepared, and their photoluminescence and thermal properties were investigated. The complexes are strongly emissive in the solid state, with the emissions being dominated by large Stokes shifts (>200 nm), which are depending on both the heterocyclic thione and the nature of the halogen. These emissions can be assigned to MLCT with some mixing of the halide-to-ligand (XL) CT characters. Simultaneous TG/DTG-DTA technique, coupled with MS for the analysis of the gaseous decomposition products, was used for two complexes with the dmpymtH ligand to determine their thermal degradation, which was found to be very complicated. In inert atmosphere the residues at 1,000 °C (verified with PXRD) were a mixture of Cu2S and CuX, while at 1,300 °C a mixture of Cu 2S and Cu. In oxygen atmosphere the residues were CuO.
Aslanidis,Gaki,Chrissafis,Lalia-Kantouri
p. 525 - 531
(2011/04/18)

NITROGEN-CONTAINING HETEROCYCLIC DERIVATIVE HAVING 11 BETA-HYDROXYSTEROID DEHYDROGENASE TYPE I INHIBITORY ACTIVITY
Disclosed is a compound which is useful as an 11β-hydroxysteroid dehydrogenase type 1 inhibitor. A compound represented by the formula: , its pharmaceutically acceptable salt, or a solvate thereof, wherein Ring A is a group represented by the formula: Ring B is optionally substituted heteroaryl, provided that optionally substituted isoxazole is excluded, or optionally substituted heterocycle, R1 is hydrogen or optionally substituted alkyl, R2 is -OR5, -SR5, halogen, halogenated alkyl or the like, R3 is optionally substituted alkyl or the like, R4 is optionally substituted alkyl or the like, R5 is optionally substituted alkyl or the like, R6 is hydrogen or the like, R7 and R8 are each independently hydrogen or the like, R10 and R11 are each independently hydrogen or the like, R12 is optionally substituted alkyl or the like, m and p are each independently integer of 1 to 3.
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(2010/04/24)

Thiosemicarbazone derivatives of copper(I): Influence of substituents (R) at N1 atom of [(C5H4N)HC2=N 3N2H-C1(=S)N1HR] in the formation of 1D or 2D networks of copper(I) complexes
Copper(I) halides with N1-substituted pyridine-2-carbaldehyde thiosemicarbazones [(C5H4N)HC2=N 3N2H-C1(=S)N1HR] in the presence of Ph3P have formed complexes of stoichiometry, [CuX(Hpytsc-N 1HR)(Ph3P)2] [X, R; Br, Me (1); Br, Et (2), Cl, Ph (3·CH3CN)]. All these complexes are characterised by elemental analysis, IR and NMR (1H, 31P) spectroscopy and X-ray crystallography. The role of substituents at N1 atom of pyridine-2-carbaldehyde thiosemicarbazones in intermolecular interactions in copper(I) complexes is described. A 1D polymer of compound 1 is formed by intermolecular CH(methyl)···π(py) interactions. The hydrogen atoms of EtN1H and ethyl group interact with the phenyl ring of PPh3 {via EtN 1H···π(Ph), H2CH (Et)···π(Ph)} to form a 1D polymer of 2. A 2D sheet arrangement of compound 3 is formed by pyridyl-phenyl (CH (py)···π(Ph)) interactions along the a axis and phenyl-phenyl [CH (Ph)···π(Ph)] interactions (phenyl at N1 with phenyl of PPh3) along the b axis. Copyright
Lobana, Tarlok S.,Sharma, Rekha,Castineiras, Alfonso,Butcher, Ray Jay
p. 2698 - 2703
(2011/02/28)

ETHER SYNTHESIS
The present invention relates to processes for preparing novel nano-copper catalyst system. The present invention also relates to manufacturing of 4-fluoro-3- phenoxy-benzaldehyde acetal employing novel nano-copper catalyst system.
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(2010/08/09)

Coinage metal derivatives of salicylaldehyde thiosemicarbazones: Synthesis, structures, bond isomerism and H-bonded networks
Reactions of salicylaldehyde thiosemicarbazone {(2-HO-C6H4)(H)C2{double bond, long}N3-N2H-C1({double bond, long}S)N1H2, H2stsc} and salicylaldehyde N-methyl
Lobana, Tarlok Singh,Khanna, Sonia,Hundal, Geeta,Kaur, Pavneet,Thakur, Bandana,Attri, Shaweta,Butcher, Ray Jay
p. 1583 - 1593
(2009/12/02)

Mono- and di-nuclear complexes of thiosemicarbazones with copper(I): Synthesis, spectroscopy and structures
Reactions of copper(I) halides with a series of thiosemicarbazones, namely, benzaldehyde thiosemicarbazone (R1R2C{double bond, long}N-NH-C({double bond, long}S)-NH2, R1 = Ph, R2 = H; Hbtsc), 2-benzoyl
Lobana, Tarlok S.,Khanna, Sonia,Hundal, Geeta,Butcher, Ray J.,Castineiras, Alfonso
p. 3899 - 3906
(2010/03/05)

1-PHENYL 1-THIO-D-GLUCITOL DERIVATIVE
A 1-phenyl 1-thio-D-glucitol compound represented by formula (I) or the like: or a pharmaceutically acceptable salt thereof or a hydrate thereof, or a pharmaceutical preparation comprising the same as an active ingredient is useful as a novel type of prophylactic or therapeutic agent for diabetes, diabetes-related diseases or diabetic complications, which inhibits both SGLT1 and SGLT2 activities to achieve not only suppression of glucose absorption from the digestive tract but also excretion of urinary sugars.
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(2009/10/01)

HETEROCYCLIC GPR40 MODULATORS
The present invention provides compounds useful, for example, for treating metabolic disorders in a subject. Such compounds have the general formula I: where the definitions of the variables are provided herein. The present invention also provides compositions that include, and methods for using, the compounds in preparing medicaments and for treating metabolic disorders such as, for example, type II diabetes.
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Page/Page column 136

(2008/06/13)

Hydrosilanes as reducing Reagents of copper salts into copper metal particles under remarkably mild conditions
Copper nanoparticles were synthesized using hydrosilanes as a reducing agent. The reaction smoothly occurred under remarkably mild conditions, i.e., room temperature. This reaction depended on the counter anions of the copper salts and the structure of the hydrosilanes, and their role is discussed.
Takahashi, Masaki,Kamada, Jun,Iwata, Kenji,Goto, Kenichi,Watanabe, Hiroshi,Tamai, Shoji
p. 168 - 170
(2009/04/07)

Metal derivatives of heterocyclic thioamides: Synthesis and crystal structures of copper complexes with 1-methyl-1,3-imidazoline-2-thione and 1,3-imidazoline-2-thione
Reactions of copper(I) halides (Cl, Br, I) with 1-methyl-1, 3-imidazoline-2-thione (mimzSH) in 1 : 2 molar ratio yielded sulfur-bridged dinuclear [Cu2X2(μ-S-mimzSH)2(η 1-S-mimzSH)2] (X = I, 1, Br, 2; Cl, 3) complexes. Copper(I) iodide with 1,3-imidazoline-2-thione (imzSH2) and Ph 3P in 1 : 1 : 1 molar ratio has also formed a sulfur-bridged dinuclear [Cu2I2(μ-S-imzSH2) 2(PPh3)2] (4) complex. The central Cu(μ-S)2Cu cores form parallelograms with unequal Cu-S bond distances {2.324(2), 2.454(3) A} (1); {2.3118(6), 2.5098(6) A} (2); {2.3075(4), 2.5218(4) A} (3); {2.3711(8), 2.4473(8) A} (4). The Cu...Cu separations, 2.759-2.877 A in complexes 1-3 are much shorter than 3.3446 A in complex 4. The weak intermolecular interactions {H 2CH...S# (2); CH...Cl# (3); NH...I# (4)} between dimeric units in complexes 2-4 lead to the formation of linear 1D polymers.
Lobana, Tarlok S.,Sharma, Renu,Sharma, Rekha,Butcher, Ray J.
p. 1785 - 1790
(2009/04/13)

N,N-dibenzyl-n-[1-cyclohexyl-3-(trimethylsilyl)-2-propynyl]-amine from cyclohexanecarbaldehyde, trimethylsilylacetylene and dibenzylamine
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Gommermann, Nina,Knochel, Paul,Rech, Jason C.,Ellman, Jonathan A.
p. 1 - 10
(2017/09/25)

PROCESS FOR THE PREPARATION OF 5-[[4-[2-(5-ETHYL-2-PYRIDINYL)ETHOXY]PHENYL] METHYL]-2,4-THIAZOLIDINEDIONE
A process for the preparation of 5-[[4-[2-(5-ethyl-2-pyridinyl)ethoxy]phenyl]methyl]-2,4-thiazolidinedione (formula 1) comprising a. reacting diazonium salt of 4-[2-(5-Ethyl-2-pyridyl) ethoxy] amino- benzene, compound of formula 2, with acrylamide, aqueous HX (wherein X is Br or Cl), under meerwein arylation conditions to yield compound of formula 3; b. condensing compound of formula 3 with thiourea to obtain compound of formula 4; and c. converting compound of formula 4 to compound of formula 1.
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Page 10-11

(2010/02/09)

1-ARYL-4-SUBSTITUTED PIPERAZINES DERIVATIVES FOR USE AS CCR1 ANTAGONISTS FOR THE TREATMENT OF INFLAMMATION AND IMMUNE DISORDERS
Compounds are provided that act as potent antagonists of the CCR1 receptor, and which have been further confirmed in animal testing for inflammation, one of the hallmark disease states for CCR1. The compounds are generally aryl piperazine derivatives and are useful in pharmaceutical compositions, methods for the treatment of CCR1-mediated diseases, and as controls in assays for the identification of competitive CCR1 antagonists.
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Page 58

(2008/06/13)

Network Motifs and Thermal Properties of Copper(I) Halide and Pseudohalide Coordination Polymers with 1,7- and 4,7-Phenanthroline
The coordination polymers .infin.(1)[CuBr(1,7-phen-κN7)] (1a), [CuI(1,7-phen)] (2a) and [(CuI)2(1,7-phen-κN7)] (2b) may be prepared by treatment of the appropriate copper(I) halide with 1,7-phenanthroline(1,7-phen) in acetonitrile. 1a exhibits staircase CuBr double chains, 2 a novel quadruple CuI chains. Their thermal properties were investigatedby DTA-TG and temperature resolved powder X-ray diffraction. On heating , both 1:1 compounds decompose to 2:1 polymers and then finally to CuBr or CuI. With 4,7-phenanthroline (4,7-phen), CuBr affords both 1:1 and 2:1 complexes (5a, 5b), CuI 1:1, 2:1 and 3:1 complexes (6a, 6b, 6c) in acetonitrile at 20°C. 5a and 6a display lamellar coordination networks, with the former containing zigzag CuBr single chains, the latter 4-membered (CuI)2 rings. A second 2:1 complex .infin.(2)[(CuI)2(4,7-phen-μ-N4,N7)] (6b') with staircase CuI double chains can be obtained by reacting CuI with 4,7-phen in a sealed glass tube at 110°C. Both 5a and 6a exhibit thermal decomposition pathways of the general type 1:1 2:1 3:1 CuX, and novel CuX triple chains are proposedfor the isostructural 3:1 polymers 5c and 6c. X-ray structures are repo rted for complexes 1a, 2b, .infin(2)[(CuCN)3(CH3CN)(1,7-phen-μ-N1,N7)] (3c*CH3CN), .infin.(1)[CuSCN(1,7-phen-κN7)] (4a), 5a, 6a and .infin.(2)[CuCN(4,7-phen-μ-N4,N7)] (7a).
Kromp, T.,Sheldrick, W. S.,Naether, C.
(2008/10/08)

Thermal and electrochemical C-X activation (X = Cl, Br, I) by the strong Lewis acid Pd3(dppm)3(Co)2+ cluster and its catalytic applications
The stoichiometric and catalytic activations of alkyl halides and acid chlorides by the unsatured Pd3(dppm)3(CO)2+ cluster (Pd32+) are investigated in detail. A series of alkyl halides (R-X; R = t-Bu, Et, Pr, Bu, allyl; X = Cl, Br, I) react slowly with Pd32+ to form the corresponding Pd3(X)+ adduct and "R+". This activation can proceed much faster if it is electrochemically induced via the formation of the paramagnetic species Pd3+. The latter is the first confidently identified paramagnetic Pd cluster. The kinetic constants extracted from the evolution of the UV-vis spectra for the thermal activation, as well as the amount of electricity to bring the activation to completion for the electrochemically induced reactions, correlate the relative C-X bond strength and the steric factors. The highly reactive "R+" species has been trapped using phenol to afford the corresponding ether. On the other hand, the acid chlorides react rapidly with Pd32+ where no induction is necessary. The analysis of the cyclic voltammograms (CV) establishes that a dissociative mechanism operates (RCOCl → RCO+ + Cl-; R = t-Bu, Ph) prior to Cl- scavenging by the Pd32+ species. For the other acid chlorides (R = n-C6H13, Me2CH, Et, Me, Pr), a second associative process (Pd32+ + RCOCl → Pd32+Cl(CO)(R)) is seen. Addition of Cu(NCMe)4+ or Ag+ leads to the abstraction of Cl- from Pd3(Cl)+ to form Pd32+ and the insoluble MCl materials (M = Cu, Ag) allowing to regenerate the starting stating unsaturated cluster, where the precipitation of MX drives the reaction. By using a copper anode, the quasi-quantitative catalytic generation of the acylium ion ("RCO+") operates cleanly and rapidly. The trapping of "RCO+" with PF6- or BF4- leads to the corresponding acid fluorides and, with an alcohol (R′OH), to the corresponding ester catalytically, under mild conditions. Attempts were made to trap the key intermediates "Pd3(Cl)+...M+" (M+ = Cu+, Ag+), which was successfully performed for Pd3(ClAg)2+, as characterized by 31P NMR, IR, and FAB mass spectrometry. During the course of this investigation, the rare case of PF6- hydrolysis has been observed, where the product PF2O2- anion is observed in the complex Pd3(PF2O2)+, where the substrate is well-located inside the cavity formed by the dppm-Ph groups above the unsatured face of the Pd32+ center. This work shows that Pd32+ is a stronger Lewis acid in CH2Cl2 and THF than AlCl3, Ag+, Cu+, and Tl+.
Lemaitre, Frederic,Lucas, Dominique,Groison, Katherine,Richard, Philippe,Mugnier, Yves,Harvey, Pierre D.
p. 5511 - 5522
(2007/10/03)

New approaches to syntheses of diethers and haloethers from cyclopentadiene
Cyclopentadiene (CPD) is oxidized by copper(II) bromide and chloride in alcohol solutions to form dialkoxy- and haloethers and exhibits a higher reactivity than butadiene. Dialkoxy-, chloroalkoxy-, and dichlorocyclopentenes are formed from CPD and CuCl2 w
Skumov, M. Ya.,Brailovskii, S. M.,Temkin, O. N.
p. 616 - 624
(2007/10/03)

Synthesis, crystal structures, and properties of the copper(I) halide coordination polymers ∞2[CuX(μ-2-chloropyrazine-N,N′)] (X = Cl, Br), ∞1[CuI(2-chloropyrazine-N)], and [Cu2I2(2-chloropyrazine)]
The new copper coordination polymers ∞2[CuX(μ-2-chloropyrazine-N,N′)] (X = Cl (I), Br (II), ∞1[CuI(2-chloropyrazine-N)] (III) and [Cu2I2(2-chloropyrazine)] (IV) has been prepared by the reaction of the copper(I) halides with 2-chloropyrazine at room-temperature or under hydrothermal conditions. The crystal structures of the 1:1 compounds I and II consist of zig-zag CuX single chains running parallel to the crystallographic a-axis which are linked by the 2-chloropyrazine spacer molecules to sheets parallel to (010). For the iodine compound III a one-dimensional structure is Found which consists of CuX double chains running parallel to the crystallographic a-axis. The thermic properties of all compounds were investigated in different gas atmospheres using simultaneously differential thermal analysis and thermogravimetry (DTA-TG) as well as temperature resolved X-ray powder diffraction. On heating, tire 1:1 compounds I and II decompose directly to the corresponding copper(I) Halides, whereas the thermal decomposition of III occcur via IV as an intermediate.
Naether, Christian,Wriedt, Mario,Je, Inke
p. 394 - 400
(2008/10/08)

1,2-metallate rearrangement: (Z)-4-(2-propenyl)-3-octen-1-OL [ 3-Octen-1-ol, 4-(2-propenyl)-, (Z)- ]
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Jarowicki, Krzysztof,Kocienski, Philip J.,Qun, Liu,Franklin, Christopher L.,Martin, Stephen F.
p. 11 - 11
(2017/09/30)

Preparation of 2-(10,11-dihydro-10-oxodibenzo-[b,f]thiepin-2-yl) propionic acid
PCT No. PCT/JP97/02922 Sec. 371 Date Feb. 17, 1999 Sec. 102(e) Date Feb. 17, 1999 PCT Filed Aug. 22, 1997 PCT Pub. No. WO98/07717 PCT Pub. Date Feb. 26, 1998A process for preparation of 2-(10,11-dihydro-10-oxodibenzo[b,f]thiepin-2-yl)propionic acid (i.e., Zaltoprofen) is performed by subjecting 2-(4-amino-3-carboxy-methylphenyl)propionic acid or its salt to diazotization and subsequent reaction with thiophenol to produce 2-(3-carboxymethyl-4-phenylthiophenyl)propionic acid or its salt, and subjecting the product to cyclization reaction. Other related processes and related compounds are also disclosed.
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(2008/06/13)