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Journal articles on the topic 'Reaktiven Intermediaten'

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Published: 4 June 2021
Last updated: 5 February 2022

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1

Carpenter, Barry K. "Dynamisches Verhalten von organischen reaktiven Intermediaten." Angewandte Chemie 110, no. 24 (December 17, 1998): 3532–43. http://dx.doi.org/10.1002/(sici)1521-3757(19981217)110:24<3532::aid-ange3532>3.0.co;2-4.

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2

Braunschweig, Holger. "Heron 8: Reaktive Intermediate und ungewöhnliche Moleküle." Nachrichten aus der Chemie 67, no. 10 (October 2019): 82. http://dx.doi.org/10.1002/nadc.20194091603.

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3

Roth, Wolfgang R., and Frank Hunold. "van-der-Waals-Komplexe, Intermediate monomolekularer Reaktionen." Liebigs Annalen 1996, no. 11 (November 1996): 1917–28. http://dx.doi.org/10.1002/jlac.199619961128.

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4

Wanner, Klaus Th. "Tetrahydro-3-pyranon: Regioselektivität bei der Bildung reaktiver Intermediate." Archiv der Pharmazie 321, no. 2 (1988): 81–83. http://dx.doi.org/10.1002/ardp.19883210208.

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5

Limberg, Christian, Ralf Köppe, and Hansgeorg Schnöckel. "Matrixisolierung und Charakterisierung eines reaktiven Intermediates bei der Olefinoxidation mit Chromylchlorid." Angewandte Chemie 110, no. 4 (February 16, 1998): 512–15. http://dx.doi.org/10.1002/(sici)1521-3757(19980216)110:4<512::aid-ange512>3.0.co;2-z.

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6

Lennox, Alastair J. J. "Meisenheimer-Komplexe in SN Ar-Reaktionen: Intermediate oder Übergangszustände?" Angewandte Chemie 130, no. 45 (October 15, 2018): 14898–900. http://dx.doi.org/10.1002/ange.201809606.

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7

Tidwell, Thomas T. "Ein Jahrhundert Ketene (1905-2005): die Entdeckung einer vielseitigen Klasse reaktiver Intermediate." Angewandte Chemie 117, no. 36 (September 12, 2005): 5926–33. http://dx.doi.org/10.1002/ange.200500098.

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8

Song, Lin, and William C. Trogler. "[(CO)3(PPh3)2OsAg(O2CCF3)], eine Modellverbindung für Intermediate bei Elektronentransfer-Reaktionen." Angewandte Chemie 104, no. 6 (June 1992): 806–8. http://dx.doi.org/10.1002/ange.19921040641.

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9

Loh, Charles C. J., and Dieter Enders. "Ausnutzung der elektrophilen Eigenschaften von Indol-Intermediaten: neue Optionen in der Planung asymmetrischer Reaktionen." Angewandte Chemie 124, no. 1 (December 8, 2011): 46–49. http://dx.doi.org/10.1002/ange.201107575.

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10

Fontain, Eric, Johannes Bauer, and Ivar Ugi. "Computerunterstützte mechanistische Analyse der Streith-Reaktion mit dem Programm RAIN." Zeitschrift für Naturforschung B 42, no. 7 (July 1, 1987): 889–91. http://dx.doi.org/10.1515/znb-1987-0716.

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Abstract An improved version of the computer program RAIN (for bilaterally generating Reaction And Intermediate Networks from educts and products; FORTRAN 77, MS-DOS) is presented. Its application is illustrated by the elaboration of a network of mechanistic pathways for the Streith reaction.
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11

Rademann, Jörg, Joachim Smerdka, Günther Jung, Philipp Grosche, and Dietmar Schmid. "Alkylierende Polymere: freigesetzte Carbenium-Ionen als vielseitige reaktive Intermediate in der Polymer-unterstützten Synthese in Lösung." Angewandte Chemie 113, no. 2 (January 19, 2001): 390–93. http://dx.doi.org/10.1002/1521-3757(20010119)113:2<390::aid-ange390>3.0.co;2-j.

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12

Hsiao, Chien-Chi, Sadiya Raja, Hsuan-Hung Liao, Iuliana Atodiresei, and Magnus Rueping. "Ortho-Chinonmethide als reaktive Intermediate in asymmetrischen Brønsted-Säure-katalysierten Cycloadditionen mit Alkenen mittels exklusiver Aktivierung des Elektrophils." Angewandte Chemie 127, no. 19 (March 17, 2015): 5854–57. http://dx.doi.org/10.1002/ange.201409850.

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13

Tolxdorff, Catherine, Dongqi Hu, Bernhard Höferth, Hartmut Schaufele, Hans Pritzkow, and Ulrich Zenneck. "Reaktive π-Komplexe der elektronenreichen Übergangsmetalle, 11. Mitteilung/ Reactive π-Complexes of the Electron Rich Transition Metal Complexes, Part 11." Zeitschrift für Naturforschung B 46, no. 6 (June 1, 1991): 729–37. http://dx.doi.org/10.1515/znb-1991-0606.

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The highly reactive arene iron complex [(η4-toluene)(η6-toluene)iron] allows the formation of C4-units from alkynes below room temperature. By this route butadiene-, cyclobutadiene-, and ferracyclopentadiene(arene)iron complexes are accessible. Synthesis, structure and the properties of one example each are reported. Ferracyclopentadienes are potential intermediates for the catalytic cyclotrimerization of alkynes in the coordination sphere of arene iron complexes.
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14

Nüske, Hanno, Mathias Noltemeyer, and Armin de Meijere. "π-Allylpalladium-Intermediate durch Carbopalladierung von Bicyclopropyliden und ihr Abfang durch Nucleophile: eine neuartige Dreikomponenten-Reaktion." Angewandte Chemie 113, no. 18 (September 17, 2001): 3509–11. http://dx.doi.org/10.1002/1521-3757(20010917)113:18<3509::aid-ange3509>3.0.co;2-v.

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15

Overman, Larry E., and Daniel J. Poon. "Asymmetrische Heck-Reaktionen über neutrale Intermediate: Verstärkung der Enantioselektion durch Halogenid-Additive und Einblicke in den Mechanismus." Angewandte Chemie 109, no. 5 (March 3, 1997): 536–38. http://dx.doi.org/10.1002/ange.19971090522.

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16

Preuss, Fritz, Uwe Fischbeck, Frank Tabellion, Jens Pemer, Walter Frank, and Guido Reiss. "Darstellung, Reaktionen und 51V-NMR-spektroskopische Untersuchungen der Imidovanadium(V)-trichloride: RN=VCl3 (R = H, SiMe3, Alkyl)." Zeitschrift für Naturforschung B 56, no. 3 (March 1, 2001): 255–62. http://dx.doi.org/10.1515/znb-2001-0307.

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Abstract Imidovanadium(V) Trichlorides The reactions of Me3SiN=VCl3 (1) with MeOH, PhOH, HCl, PyH+Cl- or LiOtBu have been studied. The reductive decomposition of 1 by hydrogen chloride in toluene yields HN=VCl3 as a labile intermediate which could be isolated only in a small amount. The syntheses of RN=VCl3 (R = neopent, nPr, cyclohex, CPh3, 1-Ad) and [(tBuN)2V2Cl4(μ-OC13H9)2] (15) are also described. All compounds obtained are characterized by 51V NMR spectroscopy, the fluorenolato complex 15 by X-ray diffraction analysis.
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17

Auner, Norbert, and Claudia Seidenschwarz. "Silaheterocyclen, VII. Reaktionen des Dichlorneopentylsilaethens mit Aldehyden / Silaheterocycles, VII. Reactions of Dichloroneopentylsilene with Aldehydes." Zeitschrift für Naturforschung B 45, no. 6 (June 1, 1990): 909–20. http://dx.doi.org/10.1515/znb-1990-0624.

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Dichloroneopentylsilene, Cl2Si=CHCH2Bu' (1), is produced from vinyltrichlorosilane (2) and LiBu' in n-pentane at —78 °C. The reactions of 1 with aromatic aldehydes like benzaldehyde and the 4-methoxy- or 4-fluoro-substituted derivatives, naphthalene-1- and -2- and 9-anthracenecarbaldehyde, furfurale and its S-analogous thiophene carbaldehyde yield 1,2-silaoxetanes by [2+2] cycloaddition with the carbonyl group. The same is true for the reactions of 1 with pivaline-, butyr- and acetaldehyde. The silaoxetanes cannot be isolated; the formation of dichlorovinylsiloxanes and the olefinic compounds R—CH=CH —CH2Bu′suggests that the cycloreversion of the Si—O four-membered ring competes with an intramolecular isomerization, evidently via formation of a zwitterionic intermediate . The product formation by coupling reactions of lithiated aldehydes and 2 is excluded by performing analogous reactions with the chlorosilanes Me2SiCl(R) (R = Cl, Me, Vi).
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18

Grobe, Joseph, Gudrun Lange, and Duc Le Van. "Reaktive E=C(p – p) π-Systeme, XXI [1] / Reactive E=C(p – p)π-Systems, XXI [1]." Zeitschrift für Naturforschung B 45, no. 3 (March 1, 1990): 299–307. http://dx.doi.org/10.1515/znb-1990-0305.

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1λ3,3λ3-Diphosphanes of the type R2PCF2P(H)CF3 [R = Me (3), Et (5), Cyclohexyl (6), Ph (7)] are formed in acceptable yields (40-75%) by reacting perfluoro-2-phosphapropene F3CP=CF2 (1) with the corresponding secondary phosphanes R2PH. By reaction with sulfur, compounds 3, 5 and 7 selectively yield the corresponding monosulfur derivates R2P(S)CF2P(H)CF3 [R = Me (8), Et (9), Ph (10)]. Treatment of 3 or 7 with dimethylamine (molar ratio 1/2) leads via HF elimination and addition of Me2NH to the aminophosphanes R2PCHFP(NMe2)CF3 [R = Me (11), Ph (12)]. In a similar procedure HF has been eliminated from 3 by 1,4-diazabicyclo[2.2.2]octane (DABCO), and on addition of methanol or ethanol to the 1,3-diphosphapropene intermediate, the alkoxy compounds Me2PCHFP(OR)CF3 [R = Me (13), Et (14)] have been obtained.
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19

Fischer, Ulrich, and Gerhard Hägele. "Anomale Michaelis-Becker-Reaktion: 1-PhenyIethan-1,2,2-trisphosphonsäure und ihre Ester / Anomalous Michaelis-Becker Reaction: 1-Phenylethan-1,2,2-triphosphonic Acid and their Esters." Zeitschrift für Naturforschung B 40, no. 9 (September 1, 1985): 1152–56. http://dx.doi.org/10.1515/znb-1985-0910.

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Sodium dialkylphosphite reacts with trichlorovinylbenzene to yield in an one-batch procedure 1-phenyl-1,2,2-ethanetrisphosphonic acid hexaalkyl esters. A carbanionic intermediate of an “anomalous Michaelis-Becker reaction” is deduced. Acidolysis of esters leads to the parent trisphosphonic acids. NMR param eters of this acid are strongly influenced by protolytic equilibrium.
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20

Schottenberger, Herwig, Michael Buchmeiser, Johann Polin, and Karl-Eberhard Schwarzhans. "Ferrocen-Derivate der Quadrat- und Propiolsäure. Synthesen und Reaktionen / Ferrocene Derivatives of Squaric Acid and Propiolic Acid. Syntheses and Reactions." Zeitschrift für Naturforschung B 48, no. 11 (November 1, 1993): 1524–32. http://dx.doi.org/10.1515/znb-1993-1110.

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Concepts for linking ferrocene derivatives with conjugated squarate and propiolate based spacer systems have been investigated. Coupling of 3,4-dichlorocyclobut-3-ene-1,2-dione (squaric acid dichloride) with cuproferrocene • dimethylsulfide resulted in 3-chloro-4-ferrocenylcyclobut-3-ene-1,2-dione (ferrocenylsemisquaric acid chloride) and 3,4-diferrocenylcyclobut-3-ene-1,2-dione. Ferrocenylsemisquaric acid chloride was further treated with ethynylferrocene and 4-ethynyl-4-(ferrocenylethynyl)tolan, respectively, to form the corresponding mixed squaric diketones, which required Zn/Pd mediated coupling conditions for sufficient conversion. The symmetrically substituted derivative of ferrocenylacetylene was prepared by the same method.Cupration and subsequent coupling of dilithioferrocene with one equivalent of iodopropiolic acid methyl ester yielded 1′-iodo- 1 -ferrocenylpropiolic acid methyl ester, and with two equivalents 1,16-bis(methoxycarbonylethynyl)biferrocene. Nucleophilic addition of secondary amines to ferrocenylpropiolic acid ethyl ester gave aminoacrylates as intermediates, which rapidly converted to ketoesters during workup. Only in the case of morpholine the corresponding adduct (ferrocenylmorpholino acrylate) could be isolated. 1,3-Diferrocenylprop-2-ene-1-one has been obtained in a Bénary reaction of lithioferrocene with 3-diethylaminoethyl acrylate in quantitative yield.In order to provide alternative syntheses of already known compounds the substitution behavior of different metallated ferrocene intermediates has also been evaluated by reaction with other acid halides (oxalyl chloride, thiophosgene, ethyl chloroformate).All new compounds, 3-chloro-4-ferrocenylcyclobut-3-ene-1,2-dione (1); 3,4-diferrocenylcyclobut-3-ene-1,2-dione (2); 3,4-diferrocenylethynylcyclobut-3-ene-1,2-dione (3); 3-ferrocenyl-4-ferrocenylethynylcyclobut-3-ene-1,2-dione (4); 3-ferrocenyl-4-ferrocenylethynylphenylethynylphenylethynylcyclobut-3-ene-1,2-dione (5); 3-(N-morpholino)-3-ferrocenylethyl acrylate (6); 3-ferrocenyl-3-ketoethyl propanoate (7); iodoferrocenylpropargylic acid methyl ester (8); 1,16-bis(methoxycarbonylethynyl)biferrocene (9) and trans-1,3-diferrocenylprop-2-ene-1-one [105 404-21-5], have been characterized by IR, MS and NMR and in several cases by UV/VIS and DSC.
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21

Kant, M., and M. Meisel. "Salze von Halogenophosphors�uren XIX [1] �ber die Bildung und den Nachweis stabiler Intermediate bei der Reaktion von Fluorid mit Phosphoroxidchlorid." Zeitschrift f�r anorganische und allgemeine Chemie 620, no. 11 (November 1994): 1937–42. http://dx.doi.org/10.1002/zaac.19946201117.

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22

Bock, Hans, and Hans Peter Wolf. "Oberflächen-Reaktionen, 9 Dehydrohalogenierungen von Halogenkohlenwasserstoffen an Raney-Nickel / Surface Reactions, 9 Dehydrohalogenation of Halohydrocarbons at Raney Nickel." Zeitschrift für Naturforschung B 44, no. 6 (June 1, 1989): 699–714. http://dx.doi.org/10.1515/znb-1989-0614.

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Raney nickel, a highly reactive and air-sensitive solid, if prepared and investigated under oxygen-free conditions, exhibits interesting catalytic properties. Using photoelectron spectroscopy for real-time gas analysis in a flow reactor, the following results are obtained with alkyl and acylhalides: Dehydrohalogenation temperatures are lowered relative to thermal HHal elimination up to 350 K. Monochloro and bromo propanes and butenes yield propene and butadiene, respectively. 1,1-Dichloro ethane or 1,1-dibromo propane only split off one HHal and form chloroethene or 1-bromopropene-2. HCl elimination from 2-methyl propionic acid chloride, expectedly, produces dimethyl ketene. Most interesting, however, is the ring opening of monobromo cyclobutane to 1-bromo-butene-3, observed already at room temperature, which strongly suggests the intermediate formation of a chemisorbed surface carbene at Raney nickel. The formation of hexadiene-1,5 as a by-product in the HCl elimination of 1-chloropropane, i. e. a surface carbene dimer, indicates their presence also in other dehydrohalogenations heterogeneously catalyzed by Raney nickel.
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23

Bock, Hans, R. Dammel, and Darryl D. DesMarteau. "Gasphasen-Reaktionen, 59 [1, 2] Die Pyrolysen von Trifluormethylazid und Hexafluorazomethan / Gas Phase Reactions, 59 [1, 2] The Pyrolyses of Trifluoromethylazide and Hexafluoroazomethane." Zeitschrift für Naturforschung B 42, no. 3 (March 1, 1987): 308–14. http://dx.doi.org/10.1515/znb-1987-0310.

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Trifluoromethyl azide decomposes in a low-pressure flow system at rather high temperatures by splitting off N2. The nature of the resulting products depends largely on the wall material of the pyrolysis tube: using molybdenum above 1120 K, FCN is observed exclusively. Neither F2C=NF nor F3C-N=N-CF3 can be detected as intermediates by comparing their PE spectra with those continuously recorded while increasing the temperature. F3C-N = N - CF3 fragments already at 870 K to give N2 and F3C-CF3. The PE spectra of F3CN3 and F2C=NF are assigned based on MNDO calculations
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24

Möhrle, H., and R. Nießen. "Reaktionen von Isochinolinium-Salzen mit Hydroxylamin-Derivaten, 1. Mitteilung. N-(Nitrophenyl)-substituierte Verbindungen/Reactions of Isoquinolinium Salts with Hydroxylamine Derivatives, 1st Communication. N-(Nitrophenyl) Substituted Compounds." Zeitschrift für Naturforschung B 54, no. 2 (February 1, 1999): 225–33. http://dx.doi.org/10.1515/znb-1999-0211.

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N-(Nitrophenyl) substituted isoquinolinium salts reacted with nucleophiles of the hydroxylamine type to different products depending on the electron withdrawing strength of the substituent. Mononitro compound 8 produced only the cyclic hydroxylamine 9a, the trinitroderivative 5 solely the ring cleaved oximes. The dinitro substance 1 held an intermediate position and gave rise to a labile cyclic hydroxylamine and a more stable ring opened Z-enamine; hydroxylamine ethers generated cyclic products which showed in dimethylsulfoxide ring chain isomerism with the tautomers.
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25

Bock, Hans, and Ralph Dammel. "Gasphasen-Reaktionen, 58 [1, 2] β-Chlorethylazid: HCl-Eliminierung und Pyrolyse / Gas Phase Reactions, 58 [1, 2] β-Chloroethyl Azide: HCl Elimination and Pyrolysis." Zeitschrift für Naturforschung B 42, no. 3 (March 1, 1987): 301–7. http://dx.doi.org/10.1515/znb-1987-0309.

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The HCl elimination from β-chloroethyl azide (1-azido-2-chloroethane) over potassium tert. butanolate at 350 K in a low pressure flow system is optimized using PE spectroscopic real-time gas analysis. The highly explosive vinyl azide formed can be purified by cool-trapping the by-products. Its subsequent and virtually hazard-free pyrolysis yields 2H-azirine, which can be isolated at temperatures below 240 K.In contrast, the direct pyrolysis of β-chloroethyl azide requires temperatures above 710 K and results in a simultaneous split-off of both HCl and N2, yielding acetonitrile as the main thermolysis product. No intermediates such as β-chloroethanimine or ketenimine are observed, a result which is interpreted in terms of chemical activation
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26

Grobe, Joseph, and Jürgen Szameitat. "Reaktive E=C(p—p)π-Systeme, XVI [1] Trimethylstannvlphosphane des Typs Me3SnP(R)CF3 (R = Me, Et) als Phosphaalken-Vorstufen / Reactive E=C(p-p)π-Systeme, XVI [1] Trimethylstannylphosphanes of the Type Me3SnP(R)CF3 (R = Me, Et) as Phosphaalkene Precursors." Zeitschrift für Naturforschung B 43, no. 4 (April 1, 1988): 427–37. http://dx.doi.org/10.1515/znb-1988-0408.

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AbstractStannylphosphanes of the type Me3SnP(R)CF3 [R = Me (1), Et (2)] have been prepared by a multistep synthesis (Fig. 1) starting either with F3CPI2 or with P(NEt2)3. Due to the alkyl sub­stituents, 1 and 2 show a higher thermal stability than the analogous perfluoroalkyl compounds Me3SnP(RF)2 (RF = CF3, C2F5). Pyrolysis of 1 and 2 at 380 °C/10-3 Torr gives the new phosphaalkenes RP=CF2 (R = Me, Et) as reactive intermediates collected at -196 °C. They polymerize on the attempt to prepare diluted solutions even at very low temperatures. In case of the ethyl derivative the product (EtPCF2)x is a colourless polymer which on heating (500-600 °C) yields a mixture of dimers (EtPCF2)2 (trans-, cis-1,3- and trans-1,2-diphosphetane; ratio 73:13,5:13,5). 1 and 2 have been used as equivalents of the phosphaalkenes RP=CF2 in one-pot reactions with 2,3-dimethylbutadiene and 1,3-cyclohexadiene, respectively. The labile P=C intermediates pro­duced at 120 °C are captured by the dienes affording the [2+4]-cycloadducts 3-6 in good yields. Oxidation with sulfur gives the corresponding phosphane sulfides 7-10 in almost quantitative yields. New compounds were characterized by spectroscopic (NMR, MS, IR) and analytical methods.
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Möhrle, H., and R. Nießen. "Reaktionen von Isochinolinium-Salzen mit Hydroxylamin-Derivaten, 3. Mitteilung. Mechanismus der Aminoxid-Bildung / Reactions of Isoquinolinium Salts with Hydroxylamine Derivatives, 3rd Communication. Mechanism of Amine Oxide Generation." Zeitschrift für Naturforschung B 54, no. 7 (July 1, 1999): 913–22. http://dx.doi.org/10.1515/znb-1999-0715.

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2-Methylpapaverinium iodide (1) reacted with hydroxylamine to papaverine-N-oxide (2), but without a detectable intermediate and only in moderate yield, caused by the steric hindrance of the 1-substituent. The ring opened product of 2-dinitrophenylisoquinolinium salt with hydroxylamine, the enamine-oxime 3b gave rise to a 3-substituted cyclic nitrone (6), when heated with triethylamine. This alkali-stable compound was transformed with acid quantitatively to isoquinoline-N-oxide (4). The enaminonitrile 9c, treated with triethylamine showed cyclization to the iminoisoquinoline 10, which by loss of nitrous acid produced the tetracyclic azaindole 11. The 2-methoxyisoquinolinium salt 16 was cleaved with O-methylhydroxylamine to the resistant di(O-methyloximes) (20a/b), unable to form the amine oxide 4. From these and former results, a mechanism for the ring opening of cycliminium salts and the recyclization to amine oxides was proposed.
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Möhrle, H., and R. Nießen. "Reaktionen von Isochinolinium-Salzen mit Hydroxylamin-Derivaten, 2. Mitteilung N-(Alkyl)- und N-(Aryl)-substituierte Verbindungen / Reactions of Isoquinolinium Salts with Hydroxylamine Derivatives, 2nd Communication N-(Alkyl) and N-(Aryl) Substituted Compounds." Zeitschrift für Naturforschung B 54, no. 4 (April 1, 1999): 532–40. http://dx.doi.org/10.1515/znb-1999-0417.

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The N -alkyl- and N -aryl-isoquinolinium salts 7, 15-17 reacted with free hydroxylamine in pyridine to give the isoquinoline-2-oxide (9) as final product. The intermediate dioximes 8 were isolated and characterized by derivatisation with acetic anhydride to the oxime ester nitrile 10. From the reaction o f 8 with trifluoroacetic anhydride/triethylam ine 3-amino-isoquinoline- 2-oxide (12) resulted after hydrolysis. Due to the electronic influence the 5-nitroisoquinolinium salts 1 -3 react faster than the 5-hydroxy derivative 20. but with the same course of conversion via dioximes to amine oxides. An optimized method for preparation of the amine oxides was developed .
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29

Bock, Hans, and Bodo Berkner. "Gasphasen-Reaktionen, 91 [1-3]Thermische und heterogen-katalysierte N2-Abspaltung aus Azo-Verbindungen R–N=N–R (R = CH3, C3H5, C6H5) / Gas Phase Reactions, 91 [1-3]Thermal and Heterogeneously Catalyzed N2 Elimination of Azo-Compounds R–N=N–R (R = CH3, C3H5, C6H5)." Zeitschrift für Naturforschung B 47, no. 11 (November 1, 1992): 1551–60. http://dx.doi.org/10.1515/znb-1992-1108.

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Thermal decompositions of azo compounds in the gas phase under reduced pressure are further investigated using photoelectron spectroscopic gas analysis. Passing diallyl, diphenyl and phenylmethyl derivatives either through a short-pathway pyrolysis (SPP) apparatus or through an external thermal reactor (ETR) results in the following fragmentations: Under nearly unimolecular conditions (SPP, 10-4 mbar pressure), diallyldiazene decomposes above 600 K to N2 and hexadiene-1,5 with the allyl radical as a detectable intermediate. The PE spectra recorded for diphenyldiazene above 1000 K (ETR, 1-2 mbar pressure) show N2, benzene, as well as traces of diphenyl. Phenylmethyldiazene yields above 800 K (SPP) predominantly N2, toluene, diphenyl and ethane with the methyl radical as the only detectable intermediate. Insertion of quartz wool into the pyrolysis tube (ETR) lowers the fragmentation temperatures, and in addition, above 850 K, HCN and aniline are PE spectroscopically identified. Surprisingly, this second reaction channel can be heterogeneously catalyzed: phenylmethyldiazene decomposes under 10-2 mbar pressure at a [Ni/SiO2] catalyst surface selectively to HCN and aniline.
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Sellmann, Dieter, and Michael Waeber. "Übergangsmetallkomplexe mit Schwefelliganden, XVIII. Synthese und Reaktionen von [Ru(L)(PPh3)dttd]-Komplexen mit kleinen Stickstoffverbindungen L = NH3, N2H4, N2H3CH3, N2H3C6H5 sowie NO+ (dttd2- = 2,3;8,9-Dibenzo-1,4,7,10-tetrathiadecan (–2))/ Transition Metal Complexes with Sulfur Ligands, XVIII. Synthesis and Reactions of [Ru(L)(PPh3)dttd] Complexes with Small Nitrogen Compounds L = NH3, N2H4, N2H3CH3, N2H3C6H5 and NO+ (dttd2- = 2,3;8,9-Dibenzo-1,4,7,10-tetrathiadecane (–2))." Zeitschrift für Naturforschung B 41, no. 7 (July 1, 1986): 877–84. http://dx.doi.org/10.1515/znb-1986-0714.

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Abstract Reaktionen von [Ru(L)(PPh3)dttd]-Komplexen mit kleinen Stickstoffverbindungen L = NH3, N2H4, N2H3CH3, N2H3C6H5 sowie NO+ (dttd2-= 2,3;8,9-Dibenzo-l,4,7,10-tetrathiadecan (—2)) Transition Metal Complexes with Sulfur Ligands, XVIII* Synthesis and Reactions of [R u(L)(PPh3)dttd] Complexes with Small Nitrogen Com pounds L = N H 3, N2H 4, N2H 3C H 3, N2H 3C6H 5 and N O + (dttd2-= 2,3;8,9-D ibenzo-l,4,7,10-tetrathiadecane (—2)) D ieter Sellmann+ Ruthenium Sulfur C om plexes, N itrogen Ligands The com plex fragment [Ru(PPh3)dttd], (dttd2-= 2,3;8,9-dibenzo-l,4,7,10-tetrath iad ecane (— 2)), coordinates small nitrogen com pounds, which have only o-as well as a-jr-donor proper­ ties. The reactions o f [Ru(PPh3)2dttd] with L — N H 3, N 2H 4, N 2H 3C H 3 and N 2H 3C6H 5, respec­ tively, give the corresponding [R u(L)(PP h3)dttd] com plexes. O xidation o f the hydrazine com ­ plex [R u(N 2H 4)(PPh3)dttd] yields [a-N 2H 2{R u(PP h3)dttd }2], the first diazene com plex in which the unstable N 2H 2 is bound to a sulfur coordinated m etal center and stabilized by a 4 c —6 e Ru— N — N — Ru system , steric shielding as well as thiolate — S---H (n,h2)---N hydrogen bridges. The reactions of the ammonia and the hydrazine com plexes, respectively, with N O PF6 yield the nitrosyl com plex [R u (N O)(PP h3)dttd]PF6 as final product; in the case o f [R u(N 2H 4)(P P h3)dttd] the intermediate formation of an azido com plex is observed IR -spectroscopically.
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31

Frank, Walter, Björn Gelhausen, Guido J. Reiß, and Risto Salzer. "Untersuchungen an Systemen des Typs PCl3/MCl3/Aren (M = Al, Ga), I. Reaktionen mit Monohalogenbenzolen; Multikern-NMR-spektroskopische Charakterisierung von Aryldichlorhydrogenphosphoniumsalzen; Struktur des para-Fluorphenyldichlorphosphonium-tetrachloroaluminats." Zeitschrift für Naturforschung B 53, no. 10 (October 1, 1998): 1149–68. http://dx.doi.org/10.1515/znb-1998-1025.

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AbstractThe reactions of the monohalobenzenes with AlCl3 (GaCl3) and PCl3 have been monitored by 31P NMR spectroscopy. Primary product of the reaction with fluorobenzene and AlCl3 is the thermolabile para-fluorophenyldichlorophosphonium tetrachloroaluminate, which was characterized by 1H, 13C, 19F, 27Al and 31P NMR spectroscopy as well as by a crystal structure analysis (space group P21/c, a = 7.0720(10), b = 12.659(3), c = 15.413(3) Å, ß = 90.93(3)°, Z = 4, T = -110 °C). For the phosphonium ion we found a very good agreement of the experimental structural parameters and those obtained by ab initio quantum chemical calculations at the B3LYP 6-31++G(d,p) level of theory. Both, the experimentally determined and the calculated structure show a significant chinoid distortion of the para-disubstituted benzene ring. From the primary product the reaction proceeds to give exclusively para-fluorophenyl-(phenyl)dichlorophosphonium tetrachloroaluminate. With GaCl3 and fluorobenzene analogous tetrachlorogallates were observed, however, some by-products were recognized: para-ftuorophenylchlorofluorophosphonium and para-fluorophenyldifluorophosphonium tetrachlorogallate at the beginning of the reaction, bis(para-fluorophenyl)chlorophosphonium tetrachlorogallate at a later stage of the reaction. The reaction of chlorobenzene with PCl3 and AlCl3 yields analogous products as compared to the reaction with fluorobenzene. However, appreciable amounts of ortho- and some meta-chlorophenyldichlorophosphonium tetrachloroaluminate are by-products. If GaCl3 is used instead of AlCl3, numerous by-products and reaction intermediates are detectable. The major one is para-chlorophenyldihydrogenchlorophosphonium tetrachlorogallate. No principal differences were observed, when AlCl3 and GaCl3, respectively, reacted with bromobenzene and PCl3 giving phenylbromodichlorophosphonium and para-bromophenylbromodichlorophosphonium salts as well as some amounts of the ortho- and meta-bromophenyl derivatives. With iodobenzene the corresponding reactions exclusively give phenyldichloroiodophosphonium tetrachloroaluminate and -gallate, respectively.
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Schneider, Jan, Eckhard Popowski, and Hans Fuhrmann. "Reaktionen von Lithiumhydridosilylamiden mit Carbonylverbindungen und Gemischen von Carbonylverbindungen und Chlortrimethylsilan / Reactions of Lithium Hydridosilylamides with Carbonyl Compounds and Mixtures of Carbonyl Compounds and Chlorotrimethylsilane." Zeitschrift für Naturforschung B 53, no. 7 (July 1, 1998): 663–72. http://dx.doi.org/10.1515/znb-1998-0703.

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Abstract The lithium hydridosilylamides Me2(H)SiN(Li)R (1: R = CMe3, 2: R = SiMe3) were allowed to react either with the non-enolizable carbonyl compounds CH2=C(Me)CHO, PhCHO and Ph2CO followed by trapping with chlorotrimethylsilane (A), or with mixtures of these carbonyl compounds and chlorotrimethylsilane (B). In the second case the course of the reactions is determined by the carbonyl compound. The composition of the reaction mixtures is nearly the same according to A and B.Main products in the reactions with the aldehydes are the corresponding imines R′CH=NR (R′ =CH2=C(Me), Ph) 3 , 4 , 8 ,9 formed by addition of the hydridosilylamides to the C = O group of the aldehydes and subsequent LiOSiMe2H elimination. Partial hydrosilylation of the aldehydes by the hydridosilanolate followed by the trimethylsilylation yields the alkoxydisiloxanes R'CH2OSiMe2OSiMe3 6 , 11. In some cases 2 partially reacts under hydrosilylation to give the alkoxydisilazanes R'CH2OSiMe2NHSiMe3 7,12.The hydrosilylation is the preferred reaction of 1 and 2 with benzophenone. The compounds Ph2CHOSiMe2NHR 13, 14 are obtained. This difference in the reaction behaviour of 1 and 2 towards the aldehydes and benzophenone is mainly due to steric reasons. Depending on the conditions the imines Ph2C=NR 20, 21 may be formed. Ph2CHOSiMe2OSiMe3 (22) is a secondary product of imine formation.In all reactions of 1 and 2 with the carbonyl compounds the corresponding alkoxysilanes R'CH2OSiMe3 (5: R' = CH2=C(Me), 6 : R' = Ph) and Ph2CHOSiMe3 (15) are generated.Compounds resulting from a reaction of 1 and 2 with chlorotrimethylsilane are produced to minor extent, but only if the molar ratio of amide to carbonyl compounds is not greater than one. The formation of a silanimine intermediate in reaction according to B is not observed.
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Müller, Jörn, Ke Qiao, Regina Schubert, and Matthias Tschampel. "π-Olefin-Iridium-Komplexe, XVIII [1] Reaktionen von Bis[cycloocta-1,5-dien-μ-chloro-iridium] mit n-Propyllithium in Gegenwart von Alkinen / π-Olefin Iridium Complexes, XVIII [1]Reactions of Bis[cycloocta-l,5-diene-μ-chloro-iridium] with n-Propyllithium in the Presence of Alkynes." Zeitschrift für Naturforschung B 48, no. 11 (November 1, 1993): 1558–64. http://dx.doi.org/10.1515/znb-1993-1114.

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The reaction of [(cod)IrCl]2 (cod = η4-cycloocta-1,5-diene) with n-C3H7Li gives non-isola-ble (cod)IrH species by β-elimination of (cod)Ir-n-C3H7 intermediates; the stable final products of further reactions with RC = CR highly depend on the nature of the substituents R. With R = Me the 6-endo-H-hexamethylcyclohexadienyl complex 1 is obtained together with the iridacyclopentadienyl compound 2 and known {[(cod)IrH]4C3H4) (3). In case of R = Et steric effects cause transfer of the hydridic hydrogen to the cod ligand, and the hexaethylbenzene species 4 is isolated which was characterized by crystal structure analysis. The reaction system with tolane again yields a 6-endo-H-cyclohexadienyl complex (5). In all cases free substituted benzenes are formed as cyclotrimerization products of the alkynes.
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Khabiyev, A. T., and B. S. Selenova. "Palladium(II)-catalyzed Suzuki–Miyaura Reactions of Arylboronic Acid with Aryl Halide in the Presence of Aryl-Ferrocenyl-Phosphines." Eurasian Chemico-Technological Journal 16, no. 1 (December 22, 2013): 79. http://dx.doi.org/10.18321/ectj172.

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<p>This study examined investigation of catalytic activity of aryl-ferrocenyl-phosphine (2-methoxyphenyl diferrocenyl phosphine (cat. 1), 2-tert-butyloxyphenyl diferrocenyl phosphine (cat. 2), 2-methoxynaphtyl diferrocenyl phosphine (cat. 3), 1,1’-bis(diphenylphosphino) ferrocene (cat. 4), phenyl diferrocenyl phosphine (cat. 5)) ligands with palladium salts as precursors in Suzuki–Miyaura reaction. Suzuki–Miyaura reaction is one of the important cross-coupling reactions and extremely powerful in forming C–C bonds. Aryl-ferrocenyl-phosphine ligands confer unprecedented activity for these processes, allowing reactions to be performed at low catalyst levels, to prepare extreme This study examined investigation of catalytic activity of aryl-ferrocenyl-phosphine (2-methoxyphenyl diferrocenyl phosphine (cat. 1), 2-tert-butyloxyphenyl diferrocenyl phosphine (cat. 2), 2-methoxynaphtyl diferrocenyl phosphine (cat. 3), 1,1’-bis(diphenylphosphino) ferrocene (cat. 4), phenyl diferrocenyl phosphine (cat. 5)) ligands with palladium salts as precursors in Suzuki–Miyaura reaction. Suzuki–Miyaura reaction is one of the important cross-coupling reactions and extremely powerful in forming C–C bonds. Aryl-ferrocenyl-phosphine ligands confer unprecedented activity for these processes, allowing reactions to be performed at low catalyst levels, to prepare extremely hindered biaryls and to be carried out, in general, also for reactions of aryl chlorides by temperature 100 ºC and pressure 1 atm. Sterically demanding and strongly Lewis-basic ferrocene-based phosphines are water- and oxygen-resistant. The Suzuki–Miyaura reaction is also an important reaction in the ground and fine organic synthesis, in the production of drugs and intermediates. To analyze the conversion of halogen aryl compounds the <sup>1</sup>H NMR spectroscopy was used. The advantage of Suzuki–Miyaura reaction in comparison with other cross-coupling reactions (Kumada-, Heck-, Heck-Carbonylation-, Murahashi-, Sonogashira-, Negishi-, Stille-reaktion, etc.) is in the usage of low toxic, water- and oxygen-insensitive thermostable organoboron compounds. As boronic acid was used phenylboronic acid and as weak base – potassium phosphate. Catalyst, precursor and weak base were dissolved in toluene. All reactions were performed under an atmosphere of nitrogen or argon. The catalytic cycle of Suzuki–Miyaura reaction typically includes three main steps: oxidative addition of the haloaromatic to catalytic active palladium (0) species, transmetalation, and reductive elimination of the product under back formation of catalytically active species. All used catalysts showed good activity with aryl bromides and weak activity with aryl chlorides.</p>
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Schneider, Jan, Eckhard Popowski, and Normen Peulecke. "Reaktionen der Lithiumhydridosilylamide Me2(H)Si-N(Li)R (R = CMe3, SiMe3) mit Chlortrimethylstannan und Chlormethylsilanen Me4–nSiCln (n = 1-3)/ Reactions of Lithium Hydridosilylamides Me2(H)Si-N(Li)R (R = CMe3, SiMe3) with Chlorotrimethylstannane and Chloromethylsilanes Me4-nSiCln (n = 1 - 3)." Zeitschrift für Naturforschung B 55, no. 10 (October 1, 2000): 924–34. http://dx.doi.org/10.1515/znb-2000-1006.

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AbstractThe under reflux conditions in n-octane stable lithium hydridosilylamides Me2(H)Si-N(Li)R (1: R = CMe3, 2: SiMe3) were allowed to react with chlorotrimethylstannane and chloromethylsilanes Me4-nSiCln (n = 1 - 3) in different molar ratios. 1 reacts with Me3SnCl in n-pentane to give the cyclodisilazane [Me2Si-NCMe3]2 (3) and Me3SnH. The reaction of 2 with Me3SnCl under the same conditions leads to a mixture of Me2 (H)Si-N(SnMe3)SiMe3 (5), [Me2Si-NSiMe3]2 (4), and to Me3SnH. In the reactions of 1 and 2 with chlorotrimethylstannane in tetrahydrofuran the corresponding N-stannylation products Me2(H)Si-N(SnMe3)R 5, 6 and very small amounts of (Me3Sn)2 are formed. The results of the reactions of 1 and 2 with Me2SiCl2 and of 1 with MeSiCl3 in n-hexane show that hydrogen-chlorine-exchange proceeds between the reactants. With Me2SiCl2 the corresponding cyclodisilazanes [Me2Si-NR]2 3, 4, N-silylation products Me2(H)Si-N(SiMe2Cl)R 7b, 8b, and Me2(H)Si-N(SiMe2H)R 7c, 8c, and the silanes Me2SiHCl and Me2SiH2 are formed, the cyclodisilazanes being the main products. 1 and MeSiCl3 produce 3, Me2(H)Si-N(R′)CMe3 (7d: R′ = SiMeCl2, 7e: R' = SiMeCIH, 7f: R′ = SiM eH2) and MeSiH3. In comparison with the reaction of 1 with Me2SiCl2 the yield of cyclodisilazane is smaller and that of N-silylated compounds is higher. The reaction behaviour of 1 towards Me2SiCl2 and MeSiCl3 in THF is comparable to that in n-hexane. No silanimine intermediates are observed in the reactions of 1 or 2 with the chloromethylsilanes Me4-nSiCln (n = 1 - 3) in the molar ratios 1:5 and 1:10.
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Müller, Jörn, Petra Escarpa Gaede, and Ke Qiao. "π-Olefin-Iridium-Komplexe, XXII [1]. C-H-Aktivierung von aromatischen und aliphatischen Solvensmolekülen RH bei der Reaktion von [Cp*IrCI2]2 mit Butadienmagnesium unter Bildung von [Cp*Ir(η3-C4H7)R] sowie Kristallstruktur von [Cp*Ir(η3-C4H7)C6H5] / π-Olefin Iridium Complexes, XXII [1]. C-H Activation of Aromatic and Aliphatic Solvent Molecules RH in the Reaction of [Cp*IrCl2]2 with Butadienemagnesium with Formation of [Cp*Ir(η3-C4H7)R], and Crystal Structure of [Cp*Ir(η3-C4H7)C6H5]." Zeitschrift für Naturforschung B 49, no. 12 (December 1, 1994): 1645–53. http://dx.doi.org/10.1515/znb-1994-1207.

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Reactions of [Cp*IrCl2]2 (Cp*=η3-C5Me5) with [MgC4H6·2 THF]n at low temperature give [Cp*Ir(η4-C4H6)] together with [Cp*Ir(η3-C4H7)R] compounds, the latter being formed via C-H activation of solvent molecules RH (RH = benzene, toluene, anisole, thiophene, furane, N-methylpyrrole, pentane, cyclohexane. THF). In the case of pyrrole, C-N -activation occurs. The ratio of syn and anti isomers of the 1-methylallyl complexes as well as the sites of C-H activation of RH were investigated by NMR spectrometry. An enantiomorphous crystal of [Cp*Ir(η3-C4H7)C6Hs] was characterized by X-ray diffraction analysis which reveals trigonal planar coordination at the Ir atom and an exo, syn conformation of the 1-methylallyl ligand. A mechanism of the reaction which involves 16-electron intermediates is discussed. The corresponding system [Cp*RhCl2]2/butadienemagnesium/RH gives only [Cp*Rh(η4-C4H6)], and no C-H activation is observed.
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Möhlenkamp, Alfons, and Rainer Mattes. "Reaktionen von Oxo-Rhenium(VII und V)-Verbindungen mit Thiobenzoylhydrazin. Kristall- und Molekülstrukturen von Re(NHNC(S)Ph)3 · DMF, Re(NHNC(S)Ph)3 · OPPh3 und [Re(NHNC(S)Ph)(NHNHC(S)Ph)2]Cl · 1/3 C2H5OH · 1/3 H2O / Reactions of Oxorhenium(VII and V) Complexes with Thiobenzoylhydrazine. Crystal and Molecular Structures of Re(NHNC(S)Ph)3 · DMF, Re(NHNC(S)Ph)3 · OPPh3 and [Re(NHNC(S)Ph)(NHNHC(S)Ph)2]Cl · 1/3 C2H5OH · 1/3 H2O." Zeitschrift für Naturforschung B 45, no. 8 (August 1, 1990): 1167–76. http://dx.doi.org/10.1515/znb-1990-0811.

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The reaction of NaReO4 with thiobenzoylhydrazine yields Re(NHNC(S)Ph)3- DMF (1). With ReOCl3(PPh3)2 thiobenzoylhydrazine reacts to give Re(NHNC(S)Ph)3 · OPPh3 (2) and in the presence of HCl to yield [Re(NHNC(S)Ph)(NHNHC(S)Ph),]Cl · 1/3 C2H5OH -1 /3 H2O (3). The structures of 1-3 have been determined. 1: monoclinic, space group P2,/c, a = 1150.1(9), b = 2050.0(9), c = 1181.0(8) pm, β = 109.62(5)°, Z = 4, 2980 reflections, R = 0.055; 2: trigonal, space group R 3, a = 1399.8(1), c = 1684.0(1) pm, Z = 3, 1419 reflections, R = 0.033; 3: monoclinic, space group P2,/c, a = 1446.8(3), b = 3220.7(5), c = 1727.1(4) pm, β = 108.42(2)°, Z = 12, 6112 reflections, R = 0.062. In 1 and 2 three N,S-chelating ligands NHNR (R = C(S)Ph) are coordinated to the central rhenium atom. The ligand structure is intermediate between a diazene and a hydrazido(2–) structure. In 3 each rhenium atom is coordinated by one NHNR and two NHNHR ligands, all N,S-chelating. The latter can be considered as protonated diazene ligands. The unit cell contains three isomeric coordination polyhedra.
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Saare, Andrea, and Lutz Dahlenburg. "Oligophosphan-Liganden, XL. trans-Cyclopentan-1,2-diyl-bis(dicyclohexylphosphan) und trans-Norbornan-2,3-diyl-bis(dicyclohexylphosphan): Synthese und Enantiomerentrennung. Reaktionen von [trans-C5H8(PCy2 )2 ]PtH(CH2CMe3 ) mit C– H-Bindungen unter achiralen und chiralen Bedingungen / Oligophosphine Ligands, XL. trans-Cyclopentane-1 ,2-diyl-bis(dicyclohexylphosphine) and trans-Norbornane-2,3-diyl-bis(dicyclohexylphosphine): Synthesis and Separation of Enantiomers. Reactions of [trans-C5H8(PCy2)2]PtH (CH2CMe3) with C - H Bonds under Achiral and Chiral Conditions." Zeitschrift für Naturforschung B 50, no. 7 (July 1, 1995): 1009–17. http://dx.doi.org/10.1515/znb-1995-0704.

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The bis(dicyclohexylphosphines) trans-C5H8(PCy2)2 (1) and trans-C7H10(PCy2)2 (11) (C5H8 = cyclopentane-1,2-diyl, C7 H10 = norbornane-2,3-diyl) were prepared by treatment of the bis(dichlorophosphines) trans-C5H8(PCl2)2 and trans -C7H10(PCl2)2 with CyMgBr. Oxidation with H2O2 in acetone gave the corresponding P,P′-dioxides, trans- C5H8[P(O)C y2]2 (2) and trans-C7H10[P(O)Cy2]2 (12) respectively. Effective optical resolution of 2 was achieved using (2S,3S )-(+)-di-O-benzoyl tartaric acid as a resolving agent. Heating (+)-2 and (-)-2 in neat Ph2SiH2 gave enantiopure 1. Reactions of 1 and 11 with (cyclo-C8H12)Pt(CH2CMe3)2 afforded the dineopentyls [transC5H8(PCy2)2]Pt(CH2CMe3)2 , 3, and [trans-C7H 10(PCy2)2]Pt(CH2CMe3)2 (13). These were further derivatized to [trans- C5H8(PCy2)2]PtH (CH2CMe3) (5), and [trans-C7 H10(PCy2)2]PtH (CH2CMe3) (15) by consecutive acidolysis (HCl or (1S)-(+)-camphor-10-sulphonic acid) and treatment with Na[BH (OMe)3] of the acido(organo) intermediates [trans-C5H8(PCy2)2]PtCl(CH2CMe3) (4) and [trans-C7H10(PCy2)2]Pt[O3SCH2C9H13 (O ) -(+ ) ]CH2CMe3 (14) (mixture of four diastereoisomers), so obtained. Thermolysis of 5 in cyclo-C6H12/PhC2H, C6H6, or Me3SiOSiMe3 led to smooth formation of [trans -C5H8(PCy2)2]PtH (R ), R = C2Ph (6 ), C6H5 (8), CH2SiMe2OSiMe3 (9), and [trans -C5H8(PCy2)2]Pt(η2-PhC ≡CH ) (7), respectively. Reactions of enantiopure complex 5, prepared from (cyclo-C8H12)Pt(CH2CMe3)2 and resolved bis(phosphine) 1 via (+ )-/(-)-3 and (+)-/(-)-4, with 2,2′-dimethylbinaphthyl and 2 ,2′ -di-t-butylbiphenyl ( 2 equiv. in cyclo-C6H12 at 68 °C) resulted in little optical induction.
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39

Möhlenkamp, Alfons, and Rainer Mattes. "Reaktionen von Oxo-Rhenium- und Diazenido-Rhenium-Komplexen mit funktionalisierten Hydrazinen. Kristall- und Molekülstrukturen von [Re(HNNC(S)Ph)(HNNHC(S)Ph)2]I · .OPPh3 · MeOH, ReO(HNNC(S)Ph)(HNNHC(S)Ph), ReCl2(PPh3)2(NNC(O)Ph)(H2NNHC(S)Ph) und ReCl2(PPh3)2(NNC(O)Ph)(H2NNHC(O)SMe) / Reactions of Oxo and Diazenido Complexes of Rhenium with Functionalized Hydrazines. Crystal and Molecular Structures of [Re(HNNC(S)Ph)(HNNHC(S)Ph)2]I · .OPPh3 · MeOH, ReO(HNNC(S)Ph)(HNNHC(S)Ph),ReCl2(PPh3)2(NNC(O)Ph)(H2NNHC(S)Ph) and ReCl2(PPh3)2(NNC(O)Ph)(H2NNHC(O)SMe)." Zeitschrift für Naturforschung B 47, no. 7 (July 1, 1992): 969–77. http://dx.doi.org/10.1515/znb-1992-0713.

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The reaction of thiobenzoylhydrazine with ReO2I(PPh3)2 and Re2O3(S2CNEt2)4 yields [Re(HNNC(S)Ph)(HNNHC(S)Ph)2]I · OPPh3 · MeOH (1), ReO(HNNC(S)PhXHNNHC(S)Ph) (2) and Re(HNNC(S)Ph)2(S2CNEt2) (3). Re(NNC(S)OMe)(S2CNEt2)2 (4) is obtained from O-methylthiocarbazate and Re2O3(S2CNEt2)4· ReCl2(PPh3)2(NNC(O)Ph) reacts with functionalized hydrazines H2NNHR (R = C(S)Ph, C(S)OMe, C(O)SMe, C(S)SMe) to the diazenidohydrazino complexes ReCl2(PPh3)2(NNC(O)Ph)(H2NNHR) (5-8). The structures of 1, 2, 5 and 6 have been determined. 1: monoclinic, space group Cc, a = 1892.1(2), b = 1227.3(1), c = 1858.4(2) pm, β = 98.34(1)°, Ζ = 4, 4544 reflections, R = 0.034; 2: monoclinic, space group P21, a = 938.6(2), b = 637.0(1), c = 1356.0(3) pm, β = 98.96(3)°, Ζ = 2, 1905 reflections, R = 0.026; 5: triclinic, space group P1̄, a = 1236.4(2), b = 1414.8(2), c = 1780.8(3) pm, α = 111.02(2)°, β = 98.19(2)°, γ = 108.29(1)°, Ζ = 2, 4576 reflections, R = 0.067; 6: triclinic, space group P1̄̄, a = 1185.9(2), b = 1195.8(2), c = 1625.4(3) pm, a = 96.36(3)°, β = 99.54(3)°, γ = 103.93(3)°, Ζ = 2, 8006 reflections, R = 0.032. 1 and 2 contain N,S-chelating HNNR and HNNHR ligands. The ligand structures can be considered as intermediate between hydrazido(2—) or (1—) and diazene or protonated diazene type structures. In 5-8 the hydrazine derived ligands are monodentate N-coordinated.
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Rademann, Jörg, and Michael Barth. "ULTRA-hochbeladene Harze durch Quervernetzung von linearem Polyethylenimin – Steigerung der Atomökonomie in der Polymer-unterstützten Chemie Wir danken der Firma Personal Chemistry GmbH, Konstanz, für die zeitweilige Überlassung eines Mikrowellen-Syntheseautomaten. J.R. bedankt sich für Unterstützung bei Prof. G. Jung und Prof. M. E. Maier, Universität Tübingen, dem Strukturfonds der Universität Tübingen, der DFG (Projekt “Reaktive Intermediate in polymeren Gelen” (Ra 895/2) und dem DFG-Graduiertenkolleg “Chemie in Interphasen” (Projekt 6, Rademann) von dem M.B. ein Stipendium erhält. Ferner danken wir Rainer Fischer, Elke Gesele, Dr. Klaus Eichele und Nicole Sessler für analytische und apparative Unterstützung." Angewandte Chemie 114, no. 16 (August 16, 2002): 3087. http://dx.doi.org/10.1002/1521-3757(20020816)114:16<3087::aid-ange3087>3.0.co;2-m.

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Warm, Katrin, Guilherme Tripodi, Erik Andris, Stefan Mebs, Uwe Kuhlmann, Holger Dau, Peter Hildebrandt, Jana Roithová, and Kallol Ray. "Spektroskopische Charakterisierung eines reaktiven [Cu 2 (μ‐OH) 2 ] 2+ Intermediates in Cu/TEMPO‐katalysierten aeroben Alkoholoxidationen." Angewandte Chemie, September 8, 2021. http://dx.doi.org/10.1002/ange.202108442.

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