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1Author    Johannes Breker, Reinhard Schmutzler, BerndD. Orbath, M. Arkus WieberRequires cookie*
 Title    Reaktionen von unsymmetrischen A5P -A 3P-Diphosphorverbindungen und von Diphosphinen (A3P -A 3P) mit ö-Chinonen Reactions of Unsymmetrical /i5P -/ 3P D iphosphorus Compounds and of Diphosphines (>l3P -A 3P) with o-Quinones  
 Abstract    The reaction o f A5P -x 3P diphosphorus com pounds with o-quinones, e.g. tetrachloro-o-benzoquinone or 2,5-di-te/7-butyl-o-benzoquinone, led not only to oxidative addition o f the o-quinone to A3P but also to insertion o f a further molecule o f o-quinone into the P -P bond (i.e. x5P -Ä 3P diphosphorus com pound and o-quinone reacted in a molar ratio 1:2). In the course o f these oxidative addition and insertion reactions the o-quinones were converted into the corresponding hydroquinones (i.e. catechols). The products o f these reactions were charac­ terized by N M R and mass spectrometric methods, and by elemental analysis. The hydrolysis o f the 1:2 addition products proceeded with cleavage o f a P -O -C (hydroquinone) bond and formation o f mononuclear products, involving Ä4P and A5P, respectively. A mechanism o f this hydrolysis is proposed and has been elucidated by independent synthesis o f some products. Diphosphines, i.e. symmetrical A3P -z 3P diphosphorus compounds, were found to react with o-quinones in the same fashion in a molar ratio 1:3, i.e. with oxidative addition o f the o-quinone to both x3P atom s and insertion o f tetrachloro-o-catechol into the P -P bond. 
  Reference    Z. Naturforsch. 45b, 1177—1186 (1990); eingegangen am 13. Oktober 1989 
  Published    1990 
  Keywords    Phosphoranes, Insertion, Oxidative Addition 
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 TEI-XML for    default:Reihe_B/45/ZNB-1990-45b-1177.pdf 
 Identifier    ZNB-1990-45b-1177 
 Volume    45 
2Author    Frank Borkenhagen, Ion Neda, H. Olger Thönnessen, PeterG. Jones, R. Einhard, Schm UtzlerRequires cookie*
 Title    Synthesis and Characterization o f 2-Substituted 5 Darstellung und Charakterisierung von 2-substituierten 5,6-Benzo-l-methyl  
 Abstract    ,6 -B en zo -l-m eth y l-3 -R -l,3 ,2 -diazaphosphorin-4-ones (R = 2-M orpholinoethyl, 1-Adam antyl) C ontaining Phosphorus w ith Coordination N um bers T hree, Four and Five The reaction of N-methylisatoic anhydride with 2-morpholinoethylamine or 1-amino-adamantane furnished N-methyl-N'-(2-morpholinoethyl)anthranilamide 1 and N-methyl-N'-(l-adamantyl)anthranilamide 2, respectively. 1 and 2 are intermediates in the synthesis of the 2-chloro-3-methyl-1,3,2 A'-diazaphosphorinones 3 and 4 by reaction of 1 and 2 with PCI,. The reaction of 3 with bis(2-chloroethyl)amine hydrochloride/triethylamine or (2-chloroethyl)amine hydrochloride/triethylamine formed the 2-substituted diazaphosphorinones 5 and 6. Hydrolysis of 3 led to the 2-oxo-A4P-compound 7. The reaction of 6 with hexafluoroacetone furnished the (A5) phosphorane 8. 5 reacted with C7H8Cr(CO)4 to form complex 9 whereas oxidation of 5 with the H20 2: urea 1:1 adduct yielded the phosphoryl compound 10. The crystal structure of 1 displays two independent molecules that show different chain conformations. Both molecules form chains parallel to the y-axis by intermolecular N (am ide)-H -0(am ide) bonds. The crystal structure of 6 shows a half-boat conformation for the phosphorinone ring; the P atom lies out of the plane. Again the molecules are linked by H-bonds into chains parallel to the y-axis. 
  Reference    Z. Naturforsch. 51b, 1627—1638 (1996); eingegangen am 14. März 1996 
  Published    1996 
  Keywords    Diazaphosphorinones, Oxidative Addition, X-Ray 
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 TEI-XML for    default:Reihe_B/51/ZNB-1996-51b-1627.pdf 
 Identifier    ZNB-1996-51b-1627 
 Volume    51 
3Author    M. D. Rausch, R. G. GastingerRequires cookie*
 Title    The Reaction of (h 5 -Cyclopentadienyl)carbonyl(triphenylphosphine)iridium and Bis(pentafluorophenyl)acetylene  
 Abstract    The reaction between (h 5 -cyclopentadienyl)carbonyl(triphenylphosphine)iridium and bis(pentafluorophenyl)acetylene has been investigated in detail. As in earlier studies involving the analogous cobalt and rhodium complexes, the metallocyclic product 1 -(h 5 -cyclopentadienyl)-l-triphenylphosphine-2,3,4,5-tetrakis-pentafluorophenyl)iridole (3) has been obtained, although in very low yield. A variety of highly fluorinated organic products have also been isolated and identified, including hexakis(pentafluorophenyl)-benzene (5), Zraws-l,2-bis(pentafluorophenyl)ethene (6) and l,2,3,4-tetrakis(pentafluoro-phenyl)naphthalene (4). The latter product has been synthesized by an independent method. Reaction mechanisms to account for the formation of 4 under these conditions are discussed. 
  Reference    Z. Naturforsch. 34b, 700—705 (1979); received January 9 1979 
  Published    1979 
  Keywords    Metallocycles, Organo-Iridium Compounds, Oxidative Addition 
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 TEI-XML for    default:Reihe_B/34/ZNB-1979-34b-0700.pdf 
 Identifier    ZNB-1979-34b-0700 
 Volume    34 
4Author    H. W. Roesky, D. Amirzadeh-AslRequires cookie*
 Title    Preparation and Reactions of Bicyclic Compounds with a Phosphorus-Phosphorus-Bond  
 Abstract    The reaction of N,N'-dimethyl-N,N'-bis(trimethylsilyl)urea with PCI3 leads to the bicyclic compound OP2[MeNCONMe]2 (3) with a direct phosphorus-phosphorus bond and to the bicycle MeNP2[MeNCONMe]2 (4). 3 reacts with tetrachloro-o-benzoquinone (TOB) to yield the spirocycle CeCl^tMeNCONMe^PaO (5) with a A 4 P-A 5 P-bond. The Lewis acids SbCls and SnCLj react with 3 to give the adducts 6 and 7. The reactions of 3 with the metal carbonyls Fe2(CO)9, Cr(CO)5THF and Cr(CO)4C7Hx lead to the metal complexes 8-10. The compounds were characterized on the basis of 31 P NMR and mass spectra. Kürzlich haben wir gezeigt, daß Reaktionen von disilylierten Harnstoffen mit Dichlorphosphanen, 
  Reference    Z. Naturforsch. 38b, 460—464 (1983); eingegangen am 14. Dezember 1982/27. Januar 1983 
  Published    1983 
  Keywords    31 P NMR, Metal Complexes, Oxidative Addition 
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 TEI-XML for    default:Reihe_B/38/ZNB-1983-38b-0460.pdf 
 Identifier    ZNB-1983-38b-0460 
 Volume    38 
5Author    Jörg Fischer, Peter Machnitzki, Othmar StelzerRequires cookie*
 Title    Chlormethylchlorphosphane mit sperrigen Substituenten -Synthese und reduktive Enthalogenierung mit Fe2(CO)9 Bulky Chloromethylchlorophosphines -Syntheses and Reductive Dehalogenation with Fe2 (CO)9  
 Abstract    Chloromethylchlorophosphines R(C1)P-CH2-C1 (R = C6H n , s<?c-C4H9, 2,4,6-R'3C6H2; R' = 
  Reference    Z. Naturforsch. 52b, 883—894 (1997); eingegangen am 18. April 1997 
  Published    1997 
  Keywords    Chloromethylchlorophosphines, Conformational Equilibria, Oxidative Addition, Reductive Dehalogenation 
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 TEI-XML for    default:Reihe_B/52/ZNB-1997-52b-0883.pdf 
 Identifier    ZNB-1997-52b-0883 
 Volume    52 
6Author    EvaS. Schmidt, Annette Schier, NorbertW. Mitzel, Hubert SchmidbaurRequires cookie*
 Title    A Simple High-Yield Synthesis of Gallium(I) Tetrachlorogallate(III) and the Reaction of Digallium Tetrachloride Tetrahydrofuran Solvate with 1,2-Diols  
 Abstract    Gallium(I) tetrachlorogallate(III) Ga[GaCU] was prepared in quantitative yield by thermal de­ composition of dichlorogallane [HGaChk, which is readily available from EtsSiH and [GaCl3]2. The reaction of catechol with solutions of this gallium(I) tetrachlorogallate(III) in tetrahydro­ furan leads to the evolution o f hydrogen gas and affords a dinuclear gallium(III) complex with penta-coordinate metal atoms chelated and bridged by mono-deprotonated catechol ligands. In the crystalline phase tetrahydrofuran molecules are hydrogen-bonded to the hydroxy groups: [G a(l,2 -0 CöH4 0 H)Cl2(C4H8 0)]2. The reaction with pinacol also gives hydrogen and the anal­ ogous product [Ga(0 CMe2CMe2 0 H)Cl2(C4Hg0)]2. The structures of the two compounds have been determined by X-ray diffraction. A mechanism of the new reaction has been proposed which involves oxidative addition of the diol to the solvate (THF)Cl2Ga-GaCl2(THF) present in the tetrahydrofuran solution to give a gallium hydride intermediate. 
  Reference    Z. Naturforsch. 56b, 337—341 (2001); received March 23 2001 
  Published    2001 
  Keywords    Gallium Halides, Gallium Diolates, Oxidative Addition 
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 TEI-XML for    default:Reihe_B/56/ZNB-2001-56b-0337.pdf 
 Identifier    ZNB-2001-56b-0337 
 Volume    56 
7Author    JohnJ. Eisch, AndrzejM. Piotrowski, AllenA. Aradi, Carl Krüger, MariaJ. Romão, D. Ruhr, F.R GRequires cookie*
 Title    Die oxidative Addition von NickeI(0)-KompIexen an Kohlenstoff-Kohlenstoff-Bindungen im Cyclobutadien. Zur Frage der Überführbarkeit von CycIobutadien-Nickel(O)-Komplexen in Nickelaringe* Oxidative Addition of Nickel(O) Complexes to Carbon-Carbon Bonds in Cyclobutadiene. The Question of the Interconvertibility of Cyclobutadiene-nickel(O) Complexes and the Nickelaring Systems  
 Abstract    Bis(triethylphosphine)(?7 4 -tetraphenylcyclobutadiene)nickel (4) was synthesized by the reduc-tion of (?7 4 -tetraphenylcyclobutadiene)nickel(II)bromide (3) with r-butyllithium in the presence of Et 3 P, and its structure was determined by X-ray crystallography. Furthermore, its reactivity towards CO, CH 3 C0 2 H, PhC=CPh, LiAlH 4 and 0 2 were investigated. l,l-Bis(triethylphos-phine)-2,3,4,5-tetraphenylnickelole (14) was synthesized from (E,E)-1,4-dilithio-l,2,3,4-tetraphenyl-l,3-butadiene (15) and bis(triethylphosphine)nickel(II)bromide. Since the resulting crystals of the nickelole were not suitable for X-ray structure determination, the compound was characterized by elemental analyses, spectral data and carbonylation to yield tetraphenylcyclo-pentadienone (6). Analogous reductions of (?; 4 -tetraphenylcyclobutadiene)nickel(II)bromide (3) in the presence of Ph 3 P or Ph 2 PCH 2 CH 2 PPh 2 , followed by carbonylation, led to 6 in 40% yield, demonstrating that about half of the cyclobutadiene rings in 3 undergo cleavage upon reduction to give the nickelole. Reactions of the dilithium reagent 15 with NiBr 2 complexed with Me 2 PCH 2 CH 2 PMe 2 , Ph 3 P or Et 2 PCH 2 CH 2 PEt 2 , led to the formation of thermolabile nickeloles, as demonstrated by carbonyla-tion which yielded 6. Warming of the nickeloles and subsequent treatment with CH 3 C0 2 H led to the formation of l,2,3,4,5,6,7,8-octaphenyl-l,3,5,7-octatetraene (8) and, in one case, octaphenyl-cyclooctatetraene (5). The relevance of these findings to the mechanism of the Reppe nickel-catalyzed oligomeriza-tion of alkynes is discussed. 
  Reference    Z. Naturforsch. 40b, 624—635 (1985); eingegangen am 15. Januar 1985 
  Published    1985 
  Keywords    Insertion Reaction, Oxidative Addition, Cyclobutadiene-Nickel(O) Complexes, Nickelacyclopentadiene, Nickelole 
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 TEI-XML for    default:Reihe_B/40/ZNB-1985-40b-0624.pdf 
 Identifier    ZNB-1985-40b-0624 
 Volume    40 
8Author    Heiko Jacobsen, Heinz-Bernhard Kraatz, Tom Ziegler, PhilipMichael BoormanRequires cookie*
 Title    Does OF2 Form Stable Transition Metal Complexes? A Density Functional Investigation of the System (OC)5Cr/OF2  
 Abstract    Theory (DFT) within the Local Density Approximation (LDA) was employed to calculate the reaction of OF2 with the metal fragment Cr(CO)5. It is demonstrated that OF2 does not show simple ligand behavior but reacts with the transition metal fragment under oxidative addition, leading to a chromium oxo-complex and transforming two cis CO into fluoroformyl ligands. We calculated this reaction to proceed without any major activation barrier and to be exothermic by about 100 kcal/mol. A possible mechanism for this reaction is discussed. 
  Reference    Z. Naturforsch. 48b, 1348—1354 (1993); received June 17 1993 
  Published    1993 
  Keywords    Oxygen Difluoride, Chromium Pentacarbonyl, Oxidative Addition, Density Functional Theory Density Functional 
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 TEI-XML for    default:Reihe_B/48/ZNB-1993-48b-1348.pdf 
 Identifier    ZNB-1993-48b-1348 
 Volume    48 
9Author    W. Preetz, G. RimkusRequires cookie*
 Title    Darstellung von trans-[PtCl4Br2] 2 -und [PtClsBr] 2 - durch oxidative Addition an [PtCl4] 2 ~ Preparation of Jrarwi-[PtCl4Br2] 2 -and [PtCl5Br] 2 -by Oxidative Addition to [PtCl4] 2 ~  
 Abstract    The oxidative addition of Br2 to [PtCl4] 2-in HBr yields almost pure frans-[PtCl4Br2] 2-, in HCl nearly pure [PtClsBr] 2-, and in CH2C12 by a quantitative and stereospecific reaction completely pure £ram-[PtCl4Br2] 2 ~. This is confirmed by ion exchange chromatography on diethylaminoethyl cellulose and by analysis of the vibrational spectra in comparison with the IR and Raman spectra of the well-known species of the series [PtClnBr6-n] 2_ , n = 0-6. The literature concerning £rans-[PtCl4Br2] 2 ~ and other mixed ligand complexes is critically discussed. 
  Reference    Z. Naturforsch. 38b, 442—445 (1983); eingegangen am 8. Dezember 1982 
  Published    1983 
  Keywords    Oxidative Addition, £rans-Tetrachlorodibromoplatinate(IV), Pentachlorobromoplatinate(IV), IR Spectra, Raman Spectra 
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 TEI-XML for    default:Reihe_B/38/ZNB-1983-38b-0442.pdf 
 Identifier    ZNB-1983-38b-0442 
 Volume    38 
10Author    F. Bitterer, D. J. Brauer, F. Dörrenbach, F. Gol, P. C. Knüppel, O. Stelzer, C. Krüger, Y.-H Tsay, FrauRequires cookie*
 Title    Reduktive  
 Abstract    Enthalogenierung von (C l,B r)R P -C H 2-P R (C l,B r) mit Fe2(CO)9 -Bildung von Komplexen mit gespannten Diphosphirangerüsten und bifunktionellen Phosphidobrücken (/i2-PR)2CH 2 Reductive Dehalogenation of (Cl, B r)R P -C H 2-P R (C l, Br) with Fe2(C O)9 -Form ation of Complexes with Strained D iphosphirane Skeletons and Bifunctional Phosphido Bridges (//2-PR)2CFI2 Reductive dehalogenation o f the bifunctional methylene bridged halogenphosphines X R P -C H 2-P R X (X = Cl, Br; R = /Pr, tBu, 2,4,6-R '3C6H 2 (R' = M e, iPr, rBu), N (S iM e3)2 and 2,6,4-rBu-,MeC6H -,-0) with diironenneacarbonyl affords phosphido com plexes with strained 
  Reference    Z. Naturforsch. 46b, 1131—1144 (1991); eingegangen am 2. Januar 1991 
  Published    1991 
  Keywords    P-Halogen Functional M ethylenebisphosphines, Oxidative Addition, Reductive D ehalogenation, Phosphido Complexes, Diastereoselective Com plexation 
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 TEI-XML for    default:Reihe_B/46/ZNB-1991-46b-1131.pdf 
 Identifier    ZNB-1991-46b-1131 
 Volume    46