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Artículos de revistas sobre el tema "Chloride abstraction"

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Autor: Grafiati
Publicado: 4 de junio de 2021
Última modificación: 20 de febrero de 2023

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1

Menkir, Mengistu Gemech y Shyi-Long Lee. "Mechanisms of metal-catalyzed cycloisomerizations of o-propargylbiaryls and o-allenylbiaryls to phenanthrenes: a DFT study". Catalysis Science & Technology 7, n.º 24 (2017): 6026–41. http://dx.doi.org/10.1039/c7cy01899a.

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DFT calculation results reveal that InCl3-catalyzed cycloisomerization of o-propargylbiphenyl proceeds via 6-exo cyclization followed by intermolecular chloride-assisted H-abstraction/proto-demetalation and intramolecular chloride-assisted H-abstraction/proto-demetalation to afford a phenanthrene skeleton.
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2

Schr�del, Hans-Peter, Alfred Schmidpeter y Heinrich N�th. "Chlorophosphaethenyl phosphonium ions by chloride abstraction from dichlorophosphanyl ylides". Heteroatom Chemistry 7, n.º 5 (1996): 355–58. http://dx.doi.org/10.1002/(sici)1098-1071(199610)7:5<355::aid-hc11>3.0.co;2-p.

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3

Conrad, Eamonn, Neil Burford, Robert McDonald y Michael J. Ferguson. "Phosphinoarsonium and Diarsonium Cations from Chloride-Abstraction-Induced Pnictogen Coupling". Inorganic Chemistry 47, n.º 8 (abril de 2008): 2952–54. http://dx.doi.org/10.1021/ic800287e.

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4

Balcar, Hynek, Alena Dosedlová y Bohumír Matyska. "Interactions of tungsten hexachloride with esters of carboxylic acids". Collection of Czechoslovak Chemical Communications 51, n.º 4 (1986): 753–62. http://dx.doi.org/10.1135/cccc19860753.

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The interactions of tungsten chlorides and oxychlorides with methyl 10-undecenoate, methyl palmitate and methyl acetate, respectively, have been investigated by UV-VIS, IR and EPR spectroscopic methods. The primary complex formed by coordination of the carbonyl group to WCl6 is converted successively to an analogical, very stable complex WOCl4.ester under the simultaneous formation of acyl chloride and methyl chloride. In the case of methyl undecenoate, the coordination reaction is accompanied by a partial reduction of WCl6 to WCl5. The latter reacts with the ester in excess to give a complex characterized by a broad EPR single line at g = 1.767 (ΔH = 7.8 mT). At higher ester-to-tungsten molar ratios, this complex undergoes deeper reduction to products containing tungsten in a lower oxidation state, and competitively, a parallel oxygen abstraction reaction yielding WOCl3, acyl chloride and methyl chloride. The participation of these reactions in the formation of active WCl6-based catalysts for methathesis of unsaturated esters is discussed.
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5

Bhasin, Menka, Indu Sharma y P. D. Sharma. "Kinetics and Mechanism of Ruthenium(III) Chloride Catalyzed Oxidation of Propane-1,3-diol by Thallium(III) in Acid Perchlorate Medium". Journal of Chemical Research 23, n.º 1 (enero de 1999): 1. http://dx.doi.org/10.1177/174751989902300106.

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6

Schleicher, David, Alexander Tronnier, Hendrik Leopold, Horst Borrmann y Thomas Strassner. "Unusual dimer formation of cyclometalated ruthenium NHC p-cymene complexes". Dalton Transactions 45, n.º 8 (2016): 3260–63. http://dx.doi.org/10.1039/c6dt00100a.

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7

Grieco, Gabriele, Olivier Blacque y Heinz Berke. "A facile synthetic route to benzimidazolium salts bearing bulky aromatic N-substituents". Beilstein Journal of Organic Chemistry 11 (17 de septiembre de 2015): 1656–66. http://dx.doi.org/10.3762/bjoc.11.182.

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An atom-economic synthetic route to benzimidazolium salts is presented. The annulated polycyclic systems: 1,3-bis(2,4,6-trimethylphenyl)-1H-benzo[d]imidazol-3-ium chloride (1-Cl), 1,3-bis(2,6-diisopropylphenyl)-1H-benzo[d]imidazol-3-ium chloride (2-Cl), 1,3-diphenyl-1H-benzo[d]imidazol-3-ium chloride (3-Cl), and 1,3-di(pyridin-2-yl)-1H-benzo[d]imidazol-3-ium chloride (4-Cl) were prepared in a two-step synthesis avoiding chromatographic work-up. In the key step triethyl orthoformate is reacted with the correspondingN1,N2-diarylbenzene-1,2-diamines and then further transformed in situ, by alkoxy abstraction using trimethylsilyl chloride (TMSCl), and concomitant imidazole ring closure.
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8

Novák, Miroslav, Jan Turek, Yaraslava Milasheuskaya, Zdeňka Růžičková, Štěpán Podzimek y Roman Jambor. "N-Donor stabilized tin(ii) cations as efficient ROP catalysts for the synthesis of linear and star-shaped PLAs via the activated monomer mechanism". Dalton Transactions 50, n.º 44 (2021): 16039–52. http://dx.doi.org/10.1039/d1dt02658e.

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N-donor stabilized tin(ii) cations were synthesized by a chloride abstraction from neutral complexes or by an auto-ionization concept. Prepared tin(ii) cations are universal catalysts for the production of linear and star-shaped PLAs via ROP.
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9

Beach, Nicholas J., Hilary A. Jenkins y Gregory J. Spivak. "Electrophilic Attack on [Cp*Cl(PPh3)Ru(CCHR)]: Carbyne Formation vs Chloride Abstraction". Organometallics 22, n.º 25 (diciembre de 2003): 5179–81. http://dx.doi.org/10.1021/om030559i.

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10

Laganà, A. y L. Ciccarelli. "Abstraction and exchange contributions to the rate constant of muonium+hydrogen chloride reaction". Hyperfine Interactions 36, n.º 1 (febrero de 1987): 59–63. http://dx.doi.org/10.1007/bf02396848.

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11

Devillard, Marc, Emmanuel Nicolas, Christian Appelt, Jana Backs, Sonia Mallet-Ladeira, Ghenwa Bouhadir, J. Chris Slootweg, Werner Uhl y Didier Bourissou. "Novel zwitterionic complexes arising from the coordination of an ambiphilic phosphorus–aluminum ligand to gold". Chem. Commun. 50, n.º 94 (2014): 14805–8. http://dx.doi.org/10.1039/c4cc06992g.

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Upon coordination of Mes2PC(CHPh)AltBu2, bridging P→M–Cl→Al coordination was observed with Rh and Pd fragments, while chloride abstraction occurred with Au. The resulting zwitterionic complexes have been fully characterized and analyzed by DFT calculations.
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12

Zhao, Xiang, Gregory K. Koyanagi y Diethard K. Bohme. "Gas-phase reactions of atomic lanthanide cations with methyl chloride — Periodicities in reactivity". Canadian Journal of Chemistry 83, n.º 11 (1 de noviembre de 2005): 1839–46. http://dx.doi.org/10.1139/v05-198.

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Room temperature reactions of lanthanide atomic cations (excluding Pm+) with CH3Cl are surveyed systematically in the gas phase using an inductively coupled plasma/selected-ion flow tube (ICP/SIFT) tandem mass spectrometer. Reaction rate coefficients are reported along with product distributions in He at 0.35 Torr (1 Torr = 133.3224 Pa) and 295 K. Cl atom transfer is the predominant reaction channel observed with all 14 lanthanide cations, but minor CH3Cl addition also occurs with the late lanthanide cations Dy+, Ho+, Er+, Tm+, and Yb+. The reaction efficiency for Cl atom transfer is shown to be governed by the energy required to promote an electron to achieve a d1s1 excited electronic configuration in which two non-f electrons are available for bonding: it decreases as the promotion energy increases and the periodic trend in reaction efficiency along the lanthanide series matches the periodic trend in the corresponding electron-promotion energy. This behaviour is consistent with a C—Cl bond insertion mechanism of the type proposed previously for insertion reactions of Ln+ cations with hydrocarbons and methyl fluoride. Direct Cl atom abstraction by a harpoonlike mechanism was excluded because of an observed noncorrelation of reaction efficiency with IE(Ln+). A remarkable Arrhenius-like correlation is observed for the dependence of reactivity on promotion energy: the early and late lanthanide cations exhibit characteristic temperatures of (1.4 ± 0.2) × 104 and (4.5 ± 0.3) × 103 K, respectively. A rapid second Cl atom transfer occurs with LaCl+, CeCl+, GdCl+, TbCl+, and LuCl+, but there was no evidence for a third chlorine atom abstraction with any of the LnCl2+ cations. Both LnCl+ and LnCl2+ add up to five methyl chloride molecules under the experimental operating conditions of the ICP/SIFT tandem mass spectrometer.Key words: lanthanide cations, Cl atom transfer, electron promotion, methyl chloride.
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13

Sharma, Hayden A., Jake Z. Essman y Eric N. Jacobsen. "Enantioselective catalytic 1,2-boronate rearrangements". Science 374, n.º 6568 (5 de noviembre de 2021): 752–57. http://dx.doi.org/10.1126/science.abm0386.

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Asymmetric carbon coupling at boron The Matteson reaction produces carbon–carbon bonds by coupling halocarbons such as widely available dichloromethane with an alkyl substituent on boron. Sharma et al . report asymmetric catalysis of this reaction. Their catalyst, derived from a chiral thiourea, a boronic ester, and an alkyl lithium base, appears to accelerate a chloride abstraction step through its lithium center. The product, still bearing a chloride, can be further modified through stereospecific displacement to generate a wide variety of trisubstituted chiral centers. —JSY
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14

Ang, KH, RH Prager y CM Williams. "The Chemistry of 5-Oxodihydroisoxazoles. XIII. Reactions of the Imino Carbene Derived From Photolysis of Ethyl 5-Oxo-2-phenyl-2,5-dihydroisoxazole-4-carboxylate". Australian Journal of Chemistry 48, n.º 3 (1995): 567. http://dx.doi.org/10.1071/ch9950567.

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Photolysis of ethyl 5-oxo-2-phenyl-2,5-dihydroisoxazole-4-carboxylate at 300 nm in acetonitrile gives a carbene which is captured efficiently by bromide, chloride, acetate and cyanate, and less efficiently by iodide, thiocyanate, cyclohexene and tetrahydrofuran. No hydrogen abstraction or reaction with double bonds was evident.
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15

Hui, Alice K., Chun-Hsing Chen, Adam M. Terwilliger, Richard L. Lord y Kenneth G. Caulton. "A tale of hydrogen abstraction, initially detectedviaX-ray diffraction". Acta Crystallographica Section C Structural Chemistry 70, n.º 3 (28 de febrero de 2014): 250–55. http://dx.doi.org/10.1107/s2053229614003234.

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Reaction of a bis-tetrazinyl pyridine pincer ligand, btzp, with a vanadium(III) reagent gives not a simple adduct but dichlorido{3-methyl-6-[6-(6-methyl-1,2,4,5-tetrazin-3-yl-κN2)pyridin-2-yl-κN]-1,4-dihydro-1,2,4,5-tetrazin-1-yl-κN1}oxidovanadium(IV) acetonitrile 2.5-solvate, [V(C11H10N9)Cl2O]·2.5CH3CN, a species which X-ray diffraction reveals to have one H atom added to one of the two tetrazinyl rings. This H atom was first revealed by a short intermolecular N...Cl contact in the unit cell and subsequently established, from difference maps, to be associated with a hydrogen bond. One chloride ligand has also been replaced by an oxide ligand in this synthetic reaction. This formula for the complex, [V(Hbtzp)Cl2O], leaves open the question of both ligand oxidation state and spin state. A computational study of all isomeric locations of the H atom shows the similarity of their energies, which is subject to perturbation by intermolecular hydrogen bonding found in X-ray work on the solid state. These density functional calculations reveal that the isomer with the H atom located as found in the solid state contains a neutral radical Hbtzp ligand and tetravalentd1V center, but that these two unpaired electrons are more stable as an open-shell singlet and hence antiferromagnetically coupled.
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16

Suter, Riccardo, Hannah Sinclair, Neil Burford, Robert McDonald, Michael J. Ferguson y Erik Schrader. "Tris(2-pyridyl)phosphine as a versatile ligand for pnictogen acceptors". Dalton Transactions 46, n.º 24 (2017): 7681–85. http://dx.doi.org/10.1039/c7dt01526g.

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We report cationic complexes of arsenic and antimony with the tris(2-pyridyl)phosphine ligand. Chloride ion abstraction from the main group halide using TMSOTf in presence of the ligand gives [P(Pyr)3Pn][OTf]3, in which the trication adopts a Janus Head type complex with a C3v symmetric cage structure and two apical lone pairs.
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17

Sitzmann, Helmut y Gotthelf Wolmershäuser. "Synthese und Kristallstruktur von Hexa(tert-butyl)bismocenium-tetrachloroaluminat / Synthesis and Crystal Structure of Hexa(tert-butyl)bismocenium Tetrachloroaluminate". Zeitschrift für Naturforschung B 52, n.º 3 (1 de marzo de 1997): 398–400. http://dx.doi.org/10.1515/znb-1997-0316.

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Abstract On chloride abstraction from chloro-bis{1,2,4-tri(tert-butyl)cyclopentadienyl}bismut(III) (2 ) with aluminum trichloride the salt [{C5H2(CMe3)3-1,2,4}2Bi]+ AlCl4- (1) has been obtained in good yield. The crystal structure of 1 shows a bismocenium cation with nearly parallel η5 - cyclopentadienyl rings (10.2° inclination of the best planes) and only a slight bending of the Cpcent -Bi-Cpcent axis (172.9°).
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18

Inomata, Koya, Takahito Watanabe y Hiromi Tobita. "Cationic Metallogermylene and Dicationic Dimetallodigermenes: Synthesis by Chloride Abstraction from N-Heterocyclic Carbene-Stabilized Chlorometallogermylenes". Journal of the American Chemical Society 136, n.º 41 (octubre de 2014): 14341–44. http://dx.doi.org/10.1021/ja506018f.

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19

Wang, Kun y James M. Mayer. "Oxidation of Isopropylcyclopropane by Chromyl Chloride: Ring-Opened Products Support a Hydrogen Atom Abstraction Mechanism". Journal of Organic Chemistry 62, n.º 13 (junio de 1997): 4248–52. http://dx.doi.org/10.1021/jo962348b.

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20

Cook, Brian J., Alexander V. Polezhaev, Chun-Hsing Chen, Maren Pink y Kenneth G. Caulton. "Deprotonation, Chloride Abstraction, and Dehydrohalogenation as Synthetic Routes to Bis-Pyrazolate Pyridyl Iron(II) Complexes". European Journal of Inorganic Chemistry 2017, n.º 34 (11 de septiembre de 2017): 3999–4012. http://dx.doi.org/10.1002/ejic.201700558.

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21

Janas, Zofia, Tadeusz Lis y Piotr Sobota. "Chloride ion abstraction from cobalt and nickel chlorides by SnCI4. Crystal structure of [Ni2(μ-Cl)3(THF)6][SnCl5(THF)]". Polyhedron 11, n.º 23 (enero de 1992): 3019–23. http://dx.doi.org/10.1016/s0277-5387(00)80170-9.

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22

Rasmussen, P., T. O. Sonnenborg, G. Goncear y K. Hinsby. "Assessing impacts of climate change, sea level rise, and drainage canals on saltwater intrusion to coastal aquifer". Hydrology and Earth System Sciences Discussions 9, n.º 7 (2 de julio de 2012): 7969–8026. http://dx.doi.org/10.5194/hessd-9-7969-2012.

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Abstract. Groundwater abstraction from coastal aquifers is vulnerable to climate change and sea level rise because both may potentially impact saltwater intrusion and hence groundwater quality depending on the hydrogeological setting. In the present study the impacts of sea level rise and changes in groundwater recharge are quantified for an island located in the Western Baltic Sea. Agricultural land dominates the western and central parts of the island, which geologically are developed as push moraine hills and a former lagoon (later wetland area) behind barrier islands to the east. The low-lying central area of the island was extensively drained and reclaimed during the second half of the 19th century. Summer cottages along the beach on the former barrier islands dominate the eastern part of the island. The main water abstraction is for holiday cottages during the summer period (June–August). The water is abstracted from 11 wells drilled to a depth of around 20 m in the upper 5–10 m of a confined chalk aquifer. Increasing chloride concentrations have been observed in several abstraction wells and in some cases the WHO drinking water standard has been exceeded. Using the modeling package MODFLOW/MT3D/SEAWAT the historical, present and future freshwater–sea water distribution is simulated. The model is calibrated against hydraulic head observations and validated against geochemical and geophysical data from new investigation wells, including borehole logs, and from an airborne transient electromagnetic survey. The impact of climate changes on saltwater intrusion is found to be sensitive to the boundary conditions of the investigated system. For the flux-controlled aquifer to the west of the drained area only changes in groundwater recharge impacts the freshwater–sea water interface whereas sea level rise do not result in increasing sea water intrusion. However, on the barrier islands to the east of the reclaimed area below which the sea is hydraulically connected to the drainage canal, and the boundary of the flow system therefore controlled, the projected changes in sea level, groundwater recharge and stage of the drainage canal all have significant impacts on saltwater intrusion and hence the chloride concentrations found in the abstraction wells.
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23

Krylov, Evgeny N. y Lyudmila V. Virzum. "Molecular electrostatic potential of the reaction center as a descriptor of the reactivity of arylsulfonyl halides". Butlerov Communications 64, n.º 11 (30 de noviembre de 2020): 33–41. http://dx.doi.org/10.37952/roi-jbc-01/20-64-11-33.

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To study the reactivity of arylsulfonyl halides, the molecular electrostatic potential (MEP) was considered for the first time as a descriptor. The reaction of hydrolysis of aromatic sulfonyl halides in the medium of mixed acetone-water solvents (according to the literature data of rate constants) was used as a model. The calculation of the structural parameters of the molecules of substituted arylsulfonyl halides was carried out using the ADF2014 software package at the level of the DFT/M06/6-311+G* (PCM) theory. It was found that the magnitude of the MEP on the sulfonyl sulfur atom is very sensitive to changes in the structure of substrates, which makes it possible to determine the change in the ratio between the rate of nucleophilic attack and anionoid abstraction of the leaving group. In particular, using the example of the hydrolysis reaction of substituted thiophenesulfonyl chlorides, it was shown that the acceleration of the reaction is observed with an increase in the donor properties of the substituents and the associated increase in the negative MEP value on the sulfonyl sulfur atom. The antibate character of the dependence of the hydrolysis constant values on the IEP value indicates that not the nucleophilic attack is the rate determining in the interaction of thiophene sulfonyl chlorides and the hydroxyl anion in this sample, but the abstraction of the chloride anion. This reaction has an unstable mechanism, when the ratio between the degree of S-nucleophile bond formation and S-halogen bond cleavage changes. This makes it possible to use MEP as a descriptor of reactivity in the hydrolysis of aryl sulfonyl halides and to elucidate the details of changes in the structure of transition states during the implementation of mechanisms other than pure SN2 mechanism.
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24

Devic, Thomas, Patrick Batail, Marc Fourmigué y Narcis Avarvari. "Unexpected Reactivity of PdCl2and PtCl2Complexes of the Unsaturated Diphosphineo-Me2TTF(PPh2)2toward Chloride Abstraction with Thallium Triflate". Inorganic Chemistry 43, n.º 10 (mayo de 2004): 3136–41. http://dx.doi.org/10.1021/ic035447y.

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25

Rasmussen, P., T. O. Sonnenborg, G. Goncear y K. Hinsby. "Assessing impacts of climate change, sea level rise, and drainage canals on saltwater intrusion to coastal aquifer". Hydrology and Earth System Sciences 17, n.º 1 (31 de enero de 2013): 421–43. http://dx.doi.org/10.5194/hess-17-421-2013.

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Abstract. Groundwater abstraction from coastal aquifers is vulnerable to climate change and sea level rise because both may potentially impact saltwater intrusion and hence groundwater quality depending on the hydrogeological setting. In the present study the impacts of sea level rise and changes in groundwater recharge are quantified for an island located in the Western Baltic Sea. The low-lying central area of the investigated part of the island was extensively drained and reclaimed during the second half of the 19th century by a system of artificial drainage canals that significantly affects the flow dynamics of the area. The drinking water, mainly for summer cottages, is abstracted from 11 wells drilled to a depth of around 20 m into the upper 5–10 m of a confined chalk aquifer, and the total pumping is only 5–6% of the drainage pumping. Increasing chloride concentrations have been observed in several abstraction wells and in some cases the WHO drinking water standard has been exceeded. Using the modeling package MODFLOW/MT3D/SEAWAT the historical, present and future freshwater-sea water distribution is simulated. The model is calibrated against hydraulic head observations and validated against geochemical and geophysical data from new investigation wells, including borehole logs, and from an airborne transient electromagnetic survey. The impact of climate changes on saltwater intrusion is found to be sensitive to the boundary conditions of the investigated system. For the flux-controlled aquifer to the west of the drained area only changes in groundwater recharge impacts the freshwater–sea water interface whereas sea level rise does not result in increasing sea water intrusion. However, on the barrier islands to the east of the reclaimed area, below which the sea is hydraulically connected to the drainage canals, and the boundary of the flow system therefore controlled, the projected changes in sea level, groundwater recharge and stage of the drainage canals all have significant impacts on saltwater intrusion and the chloride concentrations found in abstraction wells.
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26

Oberbeckmann-Winter, Nicola, Pierre Braunstein y Richard Welter. "Electrophilic Activation: Unexpected Metal−Metal Bond-Assisted Tl+Chelation by a Pt-Benzyl Moiety Instead of Chloride Abstraction". Organometallics 23, n.º 26 (diciembre de 2004): 6311–18. http://dx.doi.org/10.1021/om049282s.

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27

Brand, Alexander, Anne Hentschel, Alexander Hepp y Werner Uhl. "Dihalides of Sterically Constrained Tricyclic Phosphines, Lewis Acidity and Fluoride Affinity, Chloride Abstraction, and a Phosphonium Cation, Dimethylphosphorane". European Journal of Inorganic Chemistry 2020, n.º 4 (20 de enero de 2020): 361–69. http://dx.doi.org/10.1002/ejic.201901231.

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28

Huber, Stefan M., Tim Steinke, Patrick Wonner y Elric Engelage. "Catalytic Activation of a Carbon–Chloride Bond by Dicationic Tellurium-Based Chalcogen Bond Donors". Synthesis 53, n.º 12 (25 de enero de 2021): 2043–50. http://dx.doi.org/10.1055/a-1372-6309.

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AbstractNoncovalent interactions such as halogen bonding (XB) and chalcogen bonding (ChB) have gained increased interest over the last decade. Whereas XB-based organocatalysis has been studied in some detail by now, intermolecular ChB catalysis only emerged quite recently. Herein, bidentate cationic tellurium-based chalcogen bond donors are employed in the catalytic chloride abstraction of 1-chloroisochroman. While selenium-based ChB catalysts showed only minor activity in this given benchmark reaction, tellurium-based variants exhibited strong activity, with rate accelerations of up to 40 relative to non-chalogenated reference compounds. In general, the activity of the catalysts improved with weaker coordinating counterions, but tetrafluoroborate took part in a fluoride transfer side reaction. Catalyst stability was confirmed via a fluoro-tagged variant.
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29

Kaulmann, Ursula, Stefan R. Kaschabek y Michael Schlömann. "Mechanism of Chloride Elimination from 3-Chloro- and 2,4-Dichloro-cis,cis-Muconate: New Insight Obtained from Analysis of Muconate Cycloisomerase Variant CatB-K169A". Journal of Bacteriology 183, n.º 15 (1 de agosto de 2001): 4551–61. http://dx.doi.org/10.1128/jb.183.15.4551-4561.2001.

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ABSTRACT Chloromuconate cycloisomerases of bacteria utilizing chloroaromatic compounds are known to convert 3-chloro-cis,cis-muconate tocis-dienelactone (cis-4-carboxymethylenebut-2-en-4-olide), while usual muconate cycloisomerases transform the same substrate to the bacteriotoxic protoanemonin. Formation of protoanemonin requires that the cycloisomerization of 3-chloro-cis,cis-muconate to 4-chloromuconolactone is completed by protonation of the exocyclic carbon of the presumed enol/enolate intermediate before chloride elimination and decarboxylation take place to yield the final product. The formation ofcis-dienelactone, in contrast, could occur either by dehydrohalogenation of 4-chloromuconolactone or, more directly, by chloride elimination from the enol/enolate intermediate. To reach a better understanding of the mechanisms of chloride elimination, the proton-donating Lys169 of Pseudomonas putida muconate cycloisomerase was changed to alanine. As expected, substrates requiring protonation, such ascis,cis-muconate as well as 2- and 3-methyl-, 3-fluoro-, and 2-chloro-cis,cis-muconate, were not converted at a significant rate by the K169A variant. However, the variant was still active with 3-chloro- and 2,4-dichloro-cis,cis-muconate. Interestingly,cis-dienelactone and 2-chloro-cis-dienelactone were formed as products, whereas the wild-type enzyme forms protoanemonin and the not previously isolated 2-chloroprotoanemonin, respectively. Thus, the chloromuconate cycloisomerases may avoid (chloro-)protoanemonin formation by increasing the rate of chloride abstraction from the enol/enolate intermediate compared to that of proton addition to it.
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30

Burford, Neil, Simon Mason, Rupert E. H. Spence, J. Marc Whalen, John F. Richardson y Robin D. Rogers. "Genuine heterocycles from the acid-induced cyclization of (silylamino)(imino)(chalcogeno)phosphoranes and as a result of chloride ion abstraction from bis[bis(trimethylsilyl)amino]thiophosphoryl chloride". Organometallics 11, n.º 6 (junio de 1992): 2241–50. http://dx.doi.org/10.1021/om00042a045.

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31

Bentivegna, BriAnne, Christine I. Mariani, Jason R. Smith, Shuhua Ma, Arnold L. Rheingold y Tim J. Brunker. "Formation, Stability, and Structures of Borenium and Boronium Cations Derived from Pentamethylazaferrocene–Boranes by Hydride or Chloride Abstraction Reactions". Organometallics 33, n.º 11 (23 de mayo de 2014): 2820–30. http://dx.doi.org/10.1021/om500348u.

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32

Liaw, Ben-Jie, Tarlok S. Lobana, Ya-Wen Lin, Ju-Chun Wang y C. W. Liu. "Versatility of Dithiophosphates in the Syntheses of Copper(I) Complexes with Bis(diphenylphosphino)alkanes: Abstraction of Chloride from Dichloromethane". Inorganic Chemistry 44, n.º 26 (diciembre de 2005): 9921–29. http://dx.doi.org/10.1021/ic051166+.

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33

Bonaccorsi, Cristina, Francesco Santoro, Sebastian Gischig y Antonio Mezzetti. "Chiral Dicationic Bis(aqua) Complexes [Ru(OH2)2(PNNP)]2+: The Effect of Double Chloride Abstraction on Asymmetric Cyclopropanation". Organometallics 25, n.º 8 (abril de 2006): 2002–10. http://dx.doi.org/10.1021/om0510627.

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34

Abugideiri, Fatima, James C. Fettinger y Rinaldo Poli. "Metal-metal bonding in pentamethylcyclopentadienylmolybdenum(IV) dinuclear compounds: chloride abstraction from non-bonded Cp∗2Mo2Cl6 to afford bonded [Cp∗2Mo2Cl5]+". Inorganica Chimica Acta 229, n.º 1-2 (febrero de 1995): 445–54. http://dx.doi.org/10.1016/0020-1693(94)04279-5.

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35

Angel, Laurence A. y Kent M. Ervin. "Gas-Phase SN2 and Bromine Abstraction Reactions of Chloride Ion with Bromomethane: Reaction Cross Sections and Energy Disposal into Products". Journal of the American Chemical Society 125, n.º 4 (enero de 2003): 1014–27. http://dx.doi.org/10.1021/ja021003+.

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36

BURFORD, N., S. MASON, R. E. VON H. SPENCE, J. M. WHALEN, J. F. RICHARDSON y R. D. ROGERS. "ChemInform Abstract: “Genuine Heterocycles” from the Acid-Induced Cyclization of (Silylamino)(imino)(chalcogeno)phosphoranes and as a Result of Chloride Ion Abstraction from Bis(bis(trimethylsilyl)amino)thiophosphoryl Chloride." ChemInform 23, n.º 39 (21 de agosto de 2010): no. http://dx.doi.org/10.1002/chin.199239244.

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37

Haas, Katharina, Heinrich Nöth y Wolfgang Beck. "Metallkomplexe mit biologisch wichtigen Liganden, CXX [1]. Halbsandwich-Komplexe von Ruthenium(II) und Iridium(III) mit 3-(3-Pyridyl)-D-alaninat". Zeitschrift für Naturforschung B 54, n.º 8 (1 de agosto de 1999): 989–92. http://dx.doi.org/10.1515/znb-1999-0803.

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The reactions of the chloro bridged complexes [(ρ-cymene)RuCl2]2 and [(C5Me5)IrCl2]2 with the anion of 3-(3-pyridyl)-D-alanine (L) afford the N,O-chelate complexes (p-cymene)- Ru(L)(Cl) (1) and (C5Me5)Ir(L)(Cl) (2). Abstraction of chloride from 1 and 2 using AgSbF6 gives the dimers [(ρ-cymene)Ru(μ-L)2Ru(ρ-cymene)]2+(SbF6)2 (3) and [(C5Me5)Ir(μ-L)2- Ir(C5Me5)]2+(SbF6)2 (4) with coordination of the pyridine N atom. Complex 4 is formed in high diastereomeric excess. The structure of (C5Me5)Ir(μ-L)2Ir(C5Me5)]Cl2 (5) which contains the SIrRCRC RIr diastereoisomer in the crystal was determined by X-ray diffraction.
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38

Herberhold, Max, Thomas Schmalz y Bernd Wrackmeyer. "Tri(1-cyclohepta-2,4,6-trienyl)- phosphane, P(C7H7)3, as a Tripodal Tetradentate Ligand in Cationic, Five-coordinate Complexes of Platinum(II) and Palladium(II)". Zeitschrift für Naturforschung B 57, n.º 2 (1 de febrero de 2002): 255–58. http://dx.doi.org/10.1515/znb-2002-0220.

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Chloride abstraction, using AgPF6, from tri(1- cyclohepta-2,4,6-trienyl)phosphane platinum and palladium dichloride, [P]MCl2 [M = Pt (1), Pd (2)], affords the complexes {[P]MCl}PF6 [M = Pt (3), Pd (4)] in good yields. The central metal is coordinated by the chloro ligand, the phosphorus atom and by three η2-C=C units, one of each C7H7 ring. This assignment of a highly symmetrical C3v structure is based on a consistent set of NMR data (1H, 13C, 31P, 195Pt NMR), in agreement with NMR data of the corresponding known neutral iridium and rhodium complexes [P]MCl [M = Ir (5), Rh (6)]. The chemical shift δ103Rh of 6 was determined, and a nearly linear relationship δ195Pt / δ103Rh was established.
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39

Shahsavari, Hamid R., Reza Babadi Aghakhanpour, Mahshid Nikravesh, John Ozdemir, Mohsen Golbon Haghighi, Behrouz Notash y M. Hassan Beyzavi. "Highly Emissive Cycloplatinated(II) Complexes Obtained by the Chloride Abstraction from the Complex [Pt(ppy)(PPh3)(Cl)]: Employing Various Silver Salts". Organometallics 37, n.º 17 (30 de agosto de 2018): 2890–900. http://dx.doi.org/10.1021/acs.organomet.8b00461.

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40

Evans, William J., Laurie A. Edinger y Joseph W. Ziller. "Chloride abstraction activity of Ce(IV) nitrate and alkoxide complexes: Facile formation of [CeCl5(THF)][CeClZ(THF)5] (Z=NO3, Cl)". Polyhedron 18, n.º 10 (marzo de 1999): 1475–77. http://dx.doi.org/10.1016/s0277-5387(99)00008-x.

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41

Schreiner, Bernhard, Christian Robl, Barbara Wagner-Schuh y Wolfgang Beck. "Metal Complexes of Biologically Important Ligands, CLXXIV [1]. Palladium(II) and Platinum(II) Complexes with Schiff Bases from 2-(Diphenylphosphino)benzaldehyde and α-Amino Acid Esters". Zeitschrift für Naturforschung B 65, n.º 4 (1 de abril de 2010): 503–10. http://dx.doi.org/10.1515/znb-2010-0411.

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A series of palladium(II) and platinum(II) complexes Cl2M(P-N-O) (M = Pd, Pt) with bidentate Schiff bases (P-N-O) from 2-(diphenylphosphino)benzaldehyde and α-amino acid esters has been synthesized, using PdCl2 or K[PtCl3(C2H4)], respectively. Abstraction of chloride from Cl2M(P-N-O) (using AgBF4) has afforded the cationic complexes [(P-N-O)M(Cl)]+BF4− in which the Schiff bases function as tridentate ligands with coordination of the ester group. The structures of Cl2Pd(Ph2PC6H4C(H)=N-CH2CO2Et) and of [(Cl)Pd(Ph2PC6H4C(H)=NC(H)(CH2CH=CH2)CO2Me)]+BF4− have been determined by X-ray diffraction. Complexes (L)MCl2 and [(L)MCl]+BF4 (M = Pd, Pt) have also been prepared with the reduced Schiff base Ph2PC6H4CH2NHC(H)(CH2Ph)CO2Me.
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42

Becher Quinodoz, F., L. Maldonado, M. Blarasin, V. Lutri, A. Cabrera, M. J. Giuliano Albo y E. Matteoda. "Hydrogeological and hydrogeochemical characterization of the unconfined aquifer in the fluvio-eolian plain of Cordoba (Argentina)". Hydrology Research 50, n.º 2 (9 de octubre de 2018): 725–43. http://dx.doi.org/10.2166/nh.2018.043.

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Abstract The studied area, a vast plain located in the South of Córdoba (Argentina), presents a relief resulting from the juxtaposition of an eolian and a fluvial system. The objective of this work was to characterize the unconfined aquifer from a dynamic and a geochemical point of view, establishing relationships with lithological and geomorphological features and validating with statistical multivariate analysis (Q mode) of the geochemical data. The unconfined aquifer presents variable hydraulic gradients and groundwater velocity, both conditioned by the local relief and lithology. The aquifer showed a varied spatial geochemical pattern with fresh to salty water (0.4–10.0 g/L) and sodium bicarbonate to sodium chloride geochemical types, in some places of mixed anionic type. The statistical analysis showed two groups: Group 1 links salty-brackish groundwater of sulfate and chloride type with longitudinal dunes and lowlands with locally outcropping water. It represents evolved groundwater coming from intermediate and regional flows. Group 2 links fresh groundwater of bicarbonate type with active dunes and paleochannels. In these sites, where coarser sediments prevail, local groundwater flow cells develop as a result of recent recharge, leading to greater groundwater velocity and decreasing the transference of ions to solution. These results allow us to identify the most promising areas for freshwater abstraction.
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43

Prem, Markus, Kurt Polbom y Wolfgang Beck. "Metallkomplexe mit biologisch wichtigen Liganden, CIX [1]. Metallorganische Verbindungen von Platin(II), Ruthenium(II), Rhodium (III) und Iridium (III) mit Oxocarbonyl-N-geschützten a-Am inosäuren und L-Methionylglycinat / Metal Complexes with Biologically Important Ligands, CIX [1]. Organometallic Compounds of Platinum(II), Ruthenium(II), Rhodium(III), and Iridium(III) with Oxocarbonyl-N-protected a-Amino Acids and L-Methionylglycinate". Zeitschrift für Naturforschung B 53, n.º 12 (1 de diciembre de 1998): 1501–5. http://dx.doi.org/10.1515/znb-1998-1213.

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Abstract The reaction of cis-(Ph3P)2PtCl2 with BOC-N-glycine and FMOC-N-alanine gives the carboxylate coordinated complexes cis-(Ph3P)2 Pt(Cl)(O2CCH2NHBOC) (1) and cis- (Ph3 P)2Pt(Cl)(O2CC(H)(Me)NHFMOC (2). Chloride and proton abstraction from 1 affords the N,O-chelate complex (Ph3P)2Pt(O2CCH2NBOC) (3). From the chloro-bridged compounds [Cp*MCl2]2 (M = Rh, Ir), [(p-cymene)RuCl2]2 and BOC-N-L-MetGlyOH (L) the compounds Cp*M(Cl)2L (4, 5) and (p-cymene)Ru(Cl)2L (6 ) with the mono-dentate dipeptide are obtained which in the presence of NaOMe form O,N,S-bis(chelate) complexes 7 - 9 . The X-ray diffraction analysis of the iridium O,N,S chelate complex 8 shows a five membered and a seven membered chelate ring.
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44

Francisco, J. S. y N. Mina-Camilde. "A study of hydrogen abstraction reactions by halogen atoms with HFCO and HClCO: determination of transition state structures, barrier heights, and vibrational frequencies". Canadian Journal of Chemistry 71, n.º 1 (1 de enero de 1993): 135–40. http://dx.doi.org/10.1139/v93-019.

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Theoretical barriers and reaction energetics were determined using ab initio calculations at the PMP4/6-311 + +G** level with UMP2/6-311G** optimized geometries for hydrogen abstraction reactions of HFCO and HClCO by fluorine and chlorine atoms. The largest barriers are predicted for fluorine and chlorine atom abstractions of hydrogen from HFCO. Fluorine and chlorine atom abstractions of hydrogen from HClCO are predicted to be barrierless. The predicted barrier for fluorine atom abstraction of hydrogen from HFCO is calculated to be 1.3 kcal mol−1 and is in good agreement with the experimental value of 1.8 ± 0.4 kcal mol−1.
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45

da Silva Corrêa, Carlos M. M., Maria Augusta B. C. S. Oliveira, Maria de Lurdes S. Almeida, Paula C. M. Rodrigues, Maria M. B. Fonseca y Jorge M. A. C. Estrada. "Chlorine abstraction from arenesulphonyl chlorides by substituted phenyl radicals". J. Chem. Soc., Perkin Trans. 2, n.º 11 (1989): 1643–46. http://dx.doi.org/10.1039/p29890001643.

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46

Kuprat, Marcus, Axel Schulz, Max Thomas y Alexander Villinger. "Synthesis and characterization of a stable non-cyclic bis(amino)arsenium cation". Canadian Journal of Chemistry 96, n.º 6 (junio de 2018): 502–12. http://dx.doi.org/10.1139/cjc-2017-0420.

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The reaction of Li[Mes*NH] (1, Mes* = 2,4,6-tri-tert-butylphenyl) with aminoarsane Mes*N(H)AsCl2 (2, Mes* = 2,4,6-t-Bu3C6H2) at −80 °C resulted in the formation of bisamino(chloro)arsane (Mes*NH)2AsCl (3Cl) by elimination of LiCl. 3Cl reacted with the Lewis acids such as AlCl3, GaCl3, and Ag[X] (X = AsF6−, OTf−, BF4−; OTf = trifluoromethanesulfonate = OSO2CF3−) upon chloride ion abstraction to give salts bearing the cation [(Mes*NH)2As]+ (3[X]; X = AsF6−, OTf−, BF4−, ECl4; E = Al, Ga). 3+ represents the first NH-functionalized acyclic bis(amino)arsenium cation. The formation of the salts bearing 3+ could also be observed in the reaction of cyclo-1,3-diarsa-2,4-diazane [ClAs(μ-NMes*)]2 (4) with Lewis acids (AlCl3, GaCl3) in the presence of proton sources in solution. All presented salts 3[X] were stable at room temperature and fully characterized.
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47

REES, Martin D., Clare L. HAWKINS y Michael J. DAVIES. "Hypochlorite and superoxide radicals can act synergistically to induce fragmentation of hyaluronan and chondroitin sulphates". Biochemical Journal 381, n.º 1 (22 de junio de 2004): 175–84. http://dx.doi.org/10.1042/bj20040148.

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Activated phagocytes release the haem enzyme MPO (myeloperoxidase) and also generate superoxide radicals (O2•−), and hence H2O2, via an oxidative burst. Reaction of MPO with H2O2 in the presence of chloride ions generates HOCl (the physiological mixture of hypochlorous acid and its anion present at pH 7.4). Exposure of glycosaminoglycans to a MPO–H2O2–Cl− system or reagent HOCl generates long-lived chloramides [R-NCl-C(O)-R′] derived from the glycosamine N-acetyl functions. Decomposition of these species by transition metal ions gives polymer-derived amidyl (nitrogen-centred) radicals [R-N•-C(O)-R′], polymer-derived carbon-centred radicals and site-specific strand scission. In the present study, we have shown that exposure of glycosaminoglycan chloramides to O2•− also promotes chloramide decomposition and glycosaminoglycan fragmentation. These processes are inhibited by superoxide dismutase, metal ion chelators and the metal ion-binding protein BSA, consistent with chloramide decomposition and polymer fragmentation occurring via O2•−-dependent one-electron reduction, possibly catalysed by trace metal ions. Polymer fragmentation induced by O2•− [generated by the superoxide thermal source 1, di-(4-carboxybenzyl)hyponitrite] was demonstrated to be entirely chloramide dependent as no fragmentation occurred with the native polymers or when the chloramides were quenched by prior treatment with methionine. EPR spin-trapping experiments using 5,5-dimethyl1-pyrroline-N-oxide and 2-methyl-2-nitrosopropane have provided evidence for both O2•− and polymer-derived carbon-centred radicals as intermediates. The results obtained are consistent with a mechanism involving one-electron reduction of the chloramides to yield polymer-derived amidyl radicals, which subsequently undergo intramolecular hydrogen atom abstraction reactions to give carbon-centred radicals. The latter undergo fragmentation reactions in a site-specific manner. This synergistic damage to glycosaminoglycans induced by HOCl and O2•− may be of significance at sites of inflammation where both oxidants are generated concurrently.
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48

Musa, Sabariah, Rafidah Hamdan, Noor Aliza Ahmad, Muhammad Mujiduddin Ibrahim, Fatinah Denan y Nor Azliana Ariff. "Groundwater Eco-Distribution System for the Combination of SAT and Therapy-Electrolysis Methods". Applied Mechanics and Materials 773-774 (julio de 2015): 1340–44. http://dx.doi.org/10.4028/www.scientific.net/amm.773-774.1340.

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Abstract. Groundwater quality is generally affected by the soil type and being polluted naturally due to the soil properties itself. This paper aims to examine the effectiveness of reducing the contamination of groundwater by a simple treatment using duo soil aquifer treatment (SAT) and therapy-electrolysis processes. The SAT was applied using physical recharge well system (REWES) in deep clay medium. The filtration in the well was also properly designed to purify the abstraction and treat discharges. Other contaminations such as fluoride, nitrate, chloride and turbidity in the groundwater were treated by therapy-electrolysis techniques. This treatment method reduces more than 64% of contaminations contain without affecting its mineralogy. Therefore, these duo treatments have the best combination of methods to reduce the unneeded contaminations without affecting the groundwater purity. A groundwater eco-distribution system is useful to be implemented in terms of economic process and is ecological friendly for water distribution facilities.
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49

Blake, Alexander J., Daniela Giunta, Jonathan Shannon, Maurizio Solinas, Francesca Walzer y Simon Woodward. "In Search of New Approaches to Asymmetric Conjugate Addition: Screening Studies on the Use of [Zn(bpy*)X(R)] Reagents and α,β-Unsaturated Amide Michael Acceptors". Collection of Czechoslovak Chemical Communications 72, n.º 8 (2007): 1107–21. http://dx.doi.org/10.1135/cccc20071107.

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Conjugate additions of [Zn(bpy*)Cl(Et)] (bpy* = 4,4'-di-tert-butyl-2,2'-bipyridine) to cyclohex-2-en-1-one are promoted by ZnMe2 in 88% ee but in moderate yield under CuI phosphoramidite catalysis. In the absence of ZnMe2 the [Zn(bpy*)Cl(Et)] is inactive indicating a Schlenk-type equilibrium. Other derivatives of [Zn(bpy*)Cl(R)] (R = Bu, 4-methylbenzyl), prepared in situ from [ZnCl(R)] and the bipyridine give low yields due to competing chloride abstraction. 13C NMR studies indicate facile organo-ligand exchange between [Zn(bpy*)(Et)2] and [Zn(bpy*)Cl2] complexes. In the presence of the bipyridine, [ZnBr(allyl)] disproportionates into [Zn(bpy*)Br2] and [Zn(bpy*)(allyl)2] species. In separate studies, simple (E)-MeCH=CHCONMeR (R = Me, OMe) α,β-unsaturated amides undergo asymmetric 1,4-addition of EtMgBr in 75-99% yield and 48-79% ee in the presence of the diphosphines JosiPhos or MeDuPhos and copper(I) sources.
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50

Harvey, Pierre D., Réjean Provencher, Jonathan Gagnon, Tianle Zhang, Daniel Fortin, Karine Hierso, Marc Drouin y Steve M. Socol. "Photoinduced oxidative degradation of unsaturated M3(dppm)3CO2+ clusters (M = Pd, Pt) by chlorocarbons and chloride ion". Canadian Journal of Chemistry 74, n.º 11 (1 de noviembre de 1996): 2268–78. http://dx.doi.org/10.1139/v96-255.

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Both M3(dppm)3CO2+ clusters (M = Pd, Pt) photoreact with chlorocarbons (Cl—R; R = CCl3, CHCl2, CH2Cl, C6H5, C10H15 (adamantyl)) and chloride ion (slowly) to produce the oxidized mononuclear species M(dppm)Cl2 as a sole isolated M-coordinated inorganic product. Such reactions do not proceed in the dark, except for R = CH2C6H5. Among the organic products, the coupling compound R–R (R = C6H5) is observed along with many phosphine compounds such as P(C6H5)3. In an attempt to elucidate the photoinduced mechanism at the early stage of the phototransformations, the following have been investigated: the ground state binding constants (K11 for M = Pd in methanol), the photochemical quantum yields of cluster disappearance (Φdis for M = Pd) as a function of substrates, substrate concentrations, excitation wavelengths, solvents (ethanol vs toluene), and presence of CO, and the emission lifetimes (τe for M = Pt) at 77 K as a function of substrate concentrations (CH2Cl2 and CHCl3) in ethanol and toluene. Some of the experimental conclusions have also been corroborated theoretically using density functional theory. Geometry optimization calculations have been performed for the model compounds [Formula: see text] Pd3(PH3)62+,[Formula: see text], [Formula: see text] and Pd3(PH3)6CO3+ in their ground states. Key words: atom abstraction, photochemistry, C-Cl bond, clusters, host-guest.
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