- Formation of the heteropolynuclear complex ([NH2(C 4H9)2][Au{S2CN(C4H 9)2}2][CdCl4])n during the chemisorption of gold(III) with cadmium dibutyldithiocarbamate: Structure and thermal properties
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The chemisorption properties of cadmium dibutyldithiocarbamate with respect to [AuCl4]- in 2M HCl solutions are studied. The heterogeneous reaction of gold(III) binding affords the heteropolynuclear compound ([NH2(C4H9)2][Au{S 2CN(C4H9)2}2][CdCl 4])n (I). The molecular and crystal structures of compound I are determined from the X-ray diffraction data. Each of three ions is presented in the structure by two conformers. The irreversible decomposition of some dibutyldithiocarbamate groups is observed during the chemisorption of gold(III), which noticeably decreases the efficiency of gold binding with the sorbent studied and its sorption capacity. The study of the thermal properties of compound I shows that gold(III) is reduced to the metal during thermolysis. Pleiades Publishing, Ltd., 2010.
- Ivanov,Sergienko,Gerasimenko,Loseva,Zaeva
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- Polynuclear complexes of gold(III) of the composition ([Au(S 2CNR2)2][AuCl4]) n (R = C4H9, R2 = (CH2)5): Synthesis, supramolecular structures, and thermal behavior
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The interaction of binuclear cadmium dialkyldithiocarbamates [Cd 2(S2CNR2)4] with solutions of AuCl3 in 2M HCl gives polynuclear gold(III) complexes ([Au(S 2CNR2)2][AuCl4]) n, where R = C4H9 (I) and R2 = (CH2) 5 (II). The structures of the synthesized compounds solved by X-ray diffraction analysis are char-acterized by a complicated organization at the supramolecular level. The structures are based on polymer chains (I) and layers (II) involving isomeric cations [Au(S2CNR2) 2]+ and anions [AuCl4]-. The thermal behavior of the synthesized complexes is studied by simultaneous thermal analysis including thermogravimetry and differential scanning calorimetry. The final product of the thermal transformations of the studied complexes is shown to be reduced metallic gold.
- Ivanov,Zinkin,Gerasimenko,Sergienko
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- Structural insights into the polymorphism of bismuth(III) di-n-butyldithiocarbamate by X-ray diffraction, solid-state (13C/15N) CP-MAS NMR and DFT calculations
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Two crystalline polymorphs of a binuclear tris(di-n-butyldithiocarbamato)bismuth(III) complex, I and II, with an empirical formula of [Bi{S2CN(n-C4H9)2}3] were synthesised and characterised by X-ray diffraction (XRD), solid-state NMR and density functional theory (DFT) calculations. At the supramolecular level, these mononuclear molecular units interact in pairs via secondary Bi?S bonds, yielding binuclear formations of [Bi2{S2CN(n-C4H9)2}6]. The polymorph I (P1ˉ) contains two isomeric non-centrosymmetric binuclear molecules of [Bi2{S2CN(n-C4H9)2}6], which are related to each other as conformers, therefore having four structurally inequivalent bismuth atoms and twelve inequivalent dithiocarbamate ligands. In contrast, the structurally simpler polymorph II (P21/n) exists as a single molecular form of the corresponding centrosymmetric binuclear formation, comprising two structurally equivalent bismuth atoms and three structurally different dithiocarbamate groups. The polymorphs I and II were found to be interconvertible by altering the solvent system during the recrystallisation process. Sun et al. (2012) has reported a crystalline form of the title compound which resembles, but is not identical with, polymorph II. Experimental solid-state 13C and 15N cross-polarisation (CP) magic-angle-spinning (MAS) NMR spectra of both polymorphs I and II were in accord with the direct structural data on these complexes. Assignments of the resonance lines in the solid-state 13C and 15N NMR spectra were assisted by chemical shift calculations of the crystals using periodic DFT.
- Gowda, Vasantha,Sarma, Bipul,Laitinen, Risto S.,Larsson, Anna-Carin,Ivanov, Alexander V.,Iuga, Dinu,Lantto, Perttu,Antzutkin, Oleg N.
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- Synthesis, toxicities and bio-activities of manganese complexes with CO and H2S dual donors
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A series of H2S–CO dual-donors [Mn(CO)4CS2NR1R2] was synthesized, and evaluated from toxicity and bioactivity. The CO–H2S measuring test showed all the complexes not only released CO, but released H2S. The resulting data of cytotoxicity showed all the complexes had activities against the cell proliferation; among them, complexes 1, 2 and 7 displayed higher activities than the others, and their potencies were close to cis-platinum (DDP); whereas the precursors A1-A22 had almost no activities against all five tumor cell lines and W138 cell line proliferation. It is worth noting that complex 1 displayed the highest activity to MCF-7, complex 2 displayed the highest activity to HePG2, and complex 7 showed selectivity inhibition to both A549 and HeLa. The developmental toxicities of the complex were assessed using zebrafish embryos. The results showed complexes 1 and 2 had effect on the mortality and hatching rate of zebrafish embryos in dose-dependent manner. They caused zebrafish malformations when they were over 10 μM. Meanwhile, they displayed dose-dependent toxicities to larval zebrafish. In the test of bio-activities, complexes 1 and 2 had strong anti-inflammatory activities; they not only down-regulated the expression levels of iNOS and TNF-α up-regulated the expression of HO-1 and IL-10, but also up-regulated COX-2 levels. In contrast, the precursor compound (A1 or A2) displayed lower anti-inflammatory activity than the corresponding complex, which suggests both the CO and H2S from the complex took synergistic effects in the process of anti-inflammation. In addition, the complex showed antihypertensive effect and myocardial protection. This effect also possibly resulted from this synergistic effect. All these suggest the complexes have potential to be candidate medicines.
- Bai, Zhongjie,Zhang, Jinlong,Zhang, Qiuping,Zhang, Taofeng,Li, Jili,Zhao, Quanyi,Wang, Zhen,He, Dian,Cheng, Jie,Zhang, Jingke,Liu, Bin
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- Multiple isomerization of structural units in ion-polymeric heteronuclear gold(III)–zinc(II) complex ([Au{S2CN(C4H9)2}2]2[ZnCl4])n: Chemisorption-based synthesis, supramolecular structure (self-organization of long-period cation–cationic polymer chains), and thermal behavior
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Chemisorption of gold(III) from solutions in 2 M HCl with freshly precipitated binuclear zinc dithiocarbamate [Zn2{S2CN(C4H9)2}4] resulted in the formation of a polymeric heteronuclear gold(III)–zinc(II) dithiocarbamato-chlorido complex ([Au{S2CN(C4H9)2}2]2[ZnCl4])n (I), which was characterized by MAS 13C NMR, X-ray diffraction (CIF file CCDC no. 1526616), and simultaneous thermal analysis. Compound I isolated on a preparative scale was found to have a highly intricate supramolecular structure composed of 13 centrosymmetric and non-centrosymmetric isomeric complex cations, [Au{S2CN(C4H9)2}2]+, with 24 structurally non-equivalent BuDtc ligands, and six isomeric [ZnCl4]2– anions. The isomeric gold(III) cations perform different structural functions. Four and six cations are involved in the formation of two sorts of long-period cation–cationic chains (via pair non-valence secondary AuS bonds): (ABCDCB)n and (FGHIJK)n. The discrete E, L, and M cations and the [ZnCl4]2– complex anions are located alongside of the polymer chains and do not take part in the secondary interactions. According to simultaneous thermal analysis, thermolysis of I includes destruction of the dithiocarbamate moiety with reduction of gold to the metal in the cation and liberation of zinc chloride with partial conversion to ZnS in the anion.
- Ivanov,Loseva,Rodina,Smolentsev
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- Gold(III)-iron(III) heteropolynuclear complexes ([Au{S2CNR2}2][FeCl4]) n (R = C4H9, iso-C4H9): Chemisorption synthesis, supramolecular self-organization, and thermal behavior
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The reactions of iron(III) dibutyl and di-iso-butyl dithiocarbamates [Fe(S2CNR2)3] (R = C4H9, iso-C4H9) with anions [AuCl4]- in 2 M HCl are studied. The result of heterogeneous reactions of gold(III) chemisorption binding from a solution is the formation of gold(III)-iron(III) heteropolynuclear complexes of the ionic type. The crystal and supramolecular structures of polymer complexes ([Au{S2CN(C4H9)2}2][FeCl4]) n (I) and ([Au{S2CN(iso-C4H9)2}2][FeCl4]) n (II) are determined by X-ray diffraction analysis (CIF files CCDC 1407704 (I) and 1407802 (II)). The structure of complex I contains two centrosymmetrical structurally nonequivalent complex cations [AuS{2CN(C4H9)2}2]+ (A and B) and complex anion [FeCl4]-. Structure II is formed by three isomeric complex cations [Au{S2CN(iso-C4H9)2}2]+ (A, B, and C) and two anions [FeCl4]- related as conformers. The isomeric cations are involved in the formation of linear (?A?B?) n (in I) or zigzag (?A?B?A...C...) n (in II) polymer chains due to pairs of weak secondary interactions Au?S. The thermal behavior of the complexes is studied by simultaneous thermal analysis. Thermal destruction includes the thermolysis of the dithiocarbamate moiety of the complexes and anions [FeCl4]- with the reduction of gold(III), release of FeCl3, and partial formation of Fe2O3. The final thermolysis products are metallic gold and Fe2O3.
- Ivanov,Loseva,Rodina,Gerasimenko,Novikova
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- Dithiocarbamates combined with copper for revitalizing meropenem efficacy against NDM-1-producing Carbapenem-resistant Enterobacteriaceae
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The worldwide prevalence of NDM-1-producing Gram-negative pathogens has drastically undermined the clinical efficacy of carbapenems, prompting a need to devise an effective strategy to preserve their clinical value. Here we constructed a focused compound library of dithiocarbamates and systematically evaluated their potential synergistic antibacterial activities combined with copper. SA09-Cu exhibited excellent inhibition against a series of clinical NDM-1-producing carbapenem-resistant Enterobacteriaceae (CRE) in restoring meropenem effect, and slowed down the development of carbapenem resistance. Enzymatic kinetic and isothermal titration calorimetry studies demonstrated that SA09-Cu was a noncompetitive NDM-1 inhibitor. The electron paramagnetic resonance (EPR) and X-ray photoelectron spectroscopy (XPS) revealed a novel inhibition mechanism, which is that SA09-Cu could convert NDM-1 into an inactive state by oxidizing the Zn(II)-thiolate site of the enzyme. Importantly, SA09-Cu showed a unique redox tuning ability, and avoided to be reduced by intracellular thiols of bacteria. In vivo experiments indicated that SA09 combined with CuGlu could effectively potentiate MER's effect against NDM-1-producing E. coli (EC23) in the murine infection model. This study provides a highly promising scaffold in developing novel inhibitors to combat NDM-1-producing CREs.
- Chen, Cheng,Yang, Ke-Wu,Zhai, Le,Ding, Huan-Huan,Chigan, Jia-Zhu
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supporting information
(2021/11/20)
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- Easer and dithiocarbamate-containing mercaptopyrimidine derivative and preparation and application thereof
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The invention provides an ester and dithiocarbamate-containing mercaptopyrimidine derivative and preparation and application thereof. A preparation method specifically comprises the steps that firstly, a dialkyl amine and a carbon disulfide form dithiocarbamate salt under the alkaline condition, and then 4,6-dimethyl-2-thiopyrimidine reacts with chloropropanol, chloroacetyl chloride and dithiocarbamate salt to obtain the pyrimidine derivative lubricating oil additive as shown in the general formula I. the derivative has the advantages that the preparation method is simple, the process condition is mild, the raw materials are easy to obtain, the synthesis cost is low, and the synthesis yield is high; the prepared pyrimidine derivative lubricating oil additive can serve as an extreme pressure, anti-wear, anti-friction and anti-corrosion additive of lubricating oil, the bearing capacity of base oil can be obviously improved, the anti-wear and anti-friction performance is improved, and theadditive is an environment-friendly multifunctional lubricating oil additive.
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Paragraph 0038; 0039
(2019/10/01)
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- Dithiocarbamate-containing benzotriazole derivative and preparation method and application thereof
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The invention provides a dithiocarbamate-containing benzotriazole derivative and a preparation method and application thereof. Under the alkaline condition, dialkyl amine reacts with carbon disulfideto obtain dithiocarbamate salt, benzotriazole reacts with chloropropanol to obtain 3-(1-benzotriazolyl)propyl-1-alcohol, then 3-(1-benzotriazolyl)propyl-1-alcohol reacts with chloroacetyl chloride toobtain 3-(1-benzotriazolyl) propyl-2-chloroacetate, and finally 3-(1-benzotriazolyl)propyl-2-chloroacetate reacts with the dithiocarbamate salt to obtain the dithiocarbamate-containing benzotriazole derivative as shown in the general formula I. Accordingly, the preparation method is simple, the process condition is mild, raw materials are easy to obtain, the synthesis cost is low, the synthesis yield is high, environmental friendliness is achieved, the product can serve as an extreme pressure, anti-wear, anti-friction and anti-corrosion additive of lubricating oil to use, the bearing capacityof base oil can be obviously improved, and the anti-wear and anti-friction properties are improved.
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Paragraph 0039; 0040
(2019/10/01)
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- Photocatalytic Dehydrogenation of Formic Acid on CdS Nanorods through Ni and Co Redox Mediation under Mild Conditions
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Selective release of hydrogen from formic acid (FA) is deemed feasible to solve issues associated with the production and storage of hydrogen. Here, we present a new efficient photocatalytic system consisting of CdS nanorods (NRs), Ni, and Co to liberate hydrogen from FA. The optimized noble-metal-free catalytic system employs Ni/Co as a redox mediator to relay electrons and holes from CdS NRs to the Ni and Co, respectively, which also deters the oxidation of CdS NRs. As a result, a high hydrogen production activity of 32.6 mmol h?1 g?1 from the decomposition of FA was noted. Furthermore, the photocatalytic system exhibits sustained H2 production rate for 12 h with sequential turnover numbers surpassing 4×103, 3×103, and 2×103 for Co–Ni/CdS NRs, Ni/CdS NRs, and CoCl2/CdS NRs, respectively.
- Nasir, Jamal Abdul,Hafeez, Muhammad,Arshad, Muhammad,Ali, Naveed Zafar,Teixeira, Ivo F.,McPherson, Ian,Zia-ur-Rehman,Khan, M. Abdullah
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p. 2587 - 2592
(2018/07/31)
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- Methylene bis(dialkyldithiocarboxamide) production method
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The present invention relates to a methylene bis(dialkyldithiocarboxamide) production method, which comprises: adding secondary alkylamine to a carbon disulfide and alkali solution mixing solution in a dropwise manner, maintaining the temperature at 0-20 DEG C, increasing the temperature to 40-65 DEG C after the adding, continuously carrying out the reaction for 1-10 h, adding dichloromethane to the methylene bis(dibutyldithiocarbamate) solution in a dropwise manner at a temperature of 40-60 DEG C, increasing the temperature to 50-905 DEG C after the adding, carrying out a reaction for 2-10 h, and carrying out liquid separation, water washing and distillation to obtain the product. According to the present invention, the nitrogen protection is used, the material feeding way is not required to be changed, the high risk grade carbon disulfide is not required to be added in the dropwise manner, other solvents are not required to be added, the reaction time and the operation steps are reduced, the production is stable, the yield is significantly improved, and the product performance meets the requirement.
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Paragraph 0022
(2016/11/17)
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- CARBONIC ANHYDRASE INHIBITOR COMPRISING A DITHIOCARBAMATE
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A carbonic anhydrase inhibitor which comprises a compound of general formula: R 1RZN-CSz-M+ for use in the treatment of microbial infection, eye disease or cancer; wherein R1 and R2 are each independently selected from H or an organic substituent, or together form a ring, and optionally contain one or more heteroatoms; wherein R and R2 together comprise at least 5 carbon atoms or at least 2 carbon atoms and a heteroatom, or R2 comprises at least 4 carbon atoms; and wherein M+ comprises a monovalent cation
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Page/Page column 20
(2013/04/24)
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- Synthesis of derivatives of di-butyldithiocarbamates
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The sodium salt of dithiocarbamate (1a) is synthesized by reaction of dibutylamine with carbon disulfide and sodium hydroxide. Phenacyldibutyl- dithiocarbamate (1b) is prepared by reaction of dibutylamine with carbon disulfide and alkylating agent. The (1-benzoyl-2,2- dibutylthio)vinyl dibutyl dithiocarbamates (1c) is prepared by dithiocarboxylation of (1b) under phase transfer conditions followed by butylation. All substance (1a), (1b) and (1c) are indentified by m.p., colour, 1H NMR and IR spectra.
- Khoudary, Kamal,Mona, Sobhi,Matar, Mouhamad,Haffar, Samar
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p. 962 - 964
(2013/05/23)
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- Catalytic activity of dithioic acid copper complexes in the alkyne-azide cycloaddition
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Diverse dithioic acid copper complexes exhibit a high catalytic activity in the copper-catalyzed alkyne-azide cycloaddition using several solvents under different temperatures, showing a high efficiency with only 0.005 mmol catalyst/mmol alkyne or less. A dithioic acid copper complex derived from acetophenone was selected and used as the catalyst in the preparation of a library of 1,4-disubstituted-1,2,3-triazoles. This process occurred in high yields and good functional group tolerance.
- Velasco, Bayardo E.,Lopez-Tellez, Gustavo,Gonzalez-Rivas, Nelly,Garcia-Orozco, Ivan,Cuevas-Yanez, Erick
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p. 292 - 299
(2013/06/05)
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- Dithiocarbamates: A new class of carbonic anhydrase inhibitors. Crystallographic and kinetic investigations
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The zinc enzyme carbonic anhydrase (CA, EC 4.2.1.1) is inhibited by several classes of zinc-binders (sulfonamides, sulfamates, and sulfamides) as well as by compounds which do not interact with the metal ion (phenols, polyamines and coumarins). Here we report a new class of potent CA inhibitors which bind the zinc ion: the dithiocarbamates (DTCs). They coordinate to the zinc ion from the enzyme active site in monodentate manner and establish many favorable interactions with amino acid residues nearby. Several low nanomolar CA I, II and IX inhibitors were detected.
- Carta, Fabrizio,Aggarwal, Mayank,Maresca, Alfonso,Scozzafava, Andrea,McKenna, Robert,Supuran, Claudiu T.
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supporting information; experimental part
p. 1868 - 1870
(2012/03/11)
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- Dithiocarbamates strongly inhibit carbonic anhydrases and show antiglaucoma action in vivo
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A series of dithiocarbamates were prepared by reaction of primary/secondary amines with carbon disulfide in the presence of bases. These compounds were tested for the inhibition of four human (h) isoforms of the zinc enzyme carbonic anhydrase, CA (EC 4.2.1.1), hCA I, II, IX, and XII, involved in pathologies such as glaucoma (CA II and XII) or cancer (CA IX). Several low nanomolar inhibitors targeting these CAs were detected. The X-ray crystal structure of the hCA II adduct with morpholine dithiocarbamate evidenced the inhibition mechanism of these compounds, which coordinate to the metal ion through a sulfur atom from the dithiocarbamate zinc-binding function. Some dithiocarbamates showed an effective intraocular pressure lowering activity in an animal model of glucoma.
- Carta, Fabrizio,Aggarwal, Mayank,Maresca, Alfonso,Scozzafava, Andrea,McKenna, Robert,Masini, Emanuela,Supuran, Claudiu T.
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supporting information; experimental part
p. 1721 - 1730
(2012/05/04)
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- Preparation and characterization of a series of bromodiphenyl(N,N-dialkyldithiocarbamato)tellurium(IV) compounds where R = Me, Et, i-Pr, Bu, and of chlorodiphenyl(N,N-dibutyldithiocarbamato)telluriumm(IV) and diphenylbis(N,N-dibutyldithiocarbamato)tellurium(IV). Crystal structure of P...
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The series Ph2TeBr, where R = Bu, Pr, i-Pr, Et, and Me, as well as Ph2TeCl and Ph2Te2, where R = Bu, Pr, have been synthesized and characterized by elemental analysis and vibrational spectroscopy.Comparisons of the effect of changing R groups and halogen atoms can be made based on the two crystal structures determined herein along with earlier work.The geometry about tellurium is consistent with that of a distorted sawhorse structure where the dithiocarbamate groups are monodentate (or anisobidentate).The crystal structures of Ph2TeBr, 4, and Ph2Te2, 7, were completed.The cell parameters for 4 are a = 11.204(3) Angstroem, b = 14.106(11) Angstroem, c = 13.867(10) Angstroem, α = 99.62(6) deg, β = 102.76(5) deg, γ = 87.73(4) deg, V = 2107 Angstroem3, Z = 4, R = 0.0448, and Rw = 0.0489 and for 7 are a = 19.392(6) Angstroem, b = 9.622(2) Angstroem, c = 19.089(6) Angstroem, β = 104.70(2) deg, V = 3445(2) Angstroem3, Z = 4, R = 0.0397, and Rw = 0.0439.Nuclear magnetic resonance spectra are not simple and indicate that several species are present in solution, as rearrangements and reductive elimination take place. Key words: structure, tellurium, bromo, diphenyl, dialkyldithiocarbamato.
- Bailey, Jane H. E.,Drake, John E.,Wong, Maria L. Y.
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p. 1948 - 1956
(2007/10/02)
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