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'Phosphorus Ylides' in keywords
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1Author    K. Arl-H, Andreas Einz Dreihäupl, Hubert Bauer, SchmidbaurRequires cookie*
 Title    Bis(silylation) of Tris(dimethylamino)phosphonium Methylide  
 Abstract    Treatment of (MezNX^PCHSiMe.^ with Me.^SiOTf (OTf = triflate) affords the phospho-nium salt [(Me2N)3PCH(SiMe?)2]OTf (2a), which can be converted into the correspond­ ing ylide (Me2NbPC(SiM e3)2 (3a) in high yield using NaN(SiMe3>2. The compounds with SiMe2Ph substituents (2, 3b) are obtained following an analogous procedure. The ylide (Me2N)3PC[Si(OMe)3]2 (3c) is available in 50% yield by direct transylidation of (M eObSiOTf with (Me2N)3PCH2 in the molar ratio 2:3, with [(Me2N)3PMe]OTf as the by-product. Com­ pound 3c is a distillable liquid, but 3a,b are crystalline solids the structure of which has been determined by single crystal X-ray diffraction. Both compounds feature a trigonal planar ylidic carbon atom and short ylidic P-C and Si-C bonds. The nitrogen atoms are also in a planar configuration with non-standard orientations of the NMe2 groups at the phosphorus atoms. These data are in agreement with the results of recent quantum chemical calculations of simple prototypes which show very flat energy profiles for internal motions (rotation, inversion) of dimethylamino groups at the phosphorus atoms in phosphines and phosphoranes. 
  Reference    Z. Naturforsch. 52b, 674—678 (1997); received April 21. 1997 
  Published    1997 
  Keywords    Silylation Ylides, Phosphorus Ylides, Aminophosphines 
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 TEI-XML for    default:Reihe_B/52/ZNB-1997-52b-0674.pdf 
 Identifier    ZNB-1997-52b-0674 
 Volume    52 
2Author    T. E. Fräser, H.-J Füller, H. SchmidbaurRequires cookie*
 Title    Einige neue Iridium-Komplexe von Phosphor-yliden Some New Iridium Complexes of Phosphorus Ylides  
 Abstract    From the iridium complexes [(l,5-C8Hi2)IrCl]2, [(C8H14)2IrCl]2 and [(C6H5)3P]2lr(CO)Cl, and the ylides (CH3)3P = CH2 and (CH3)3P = N-P(CH3)2 = CH2, a number of organoiridium compounds has been synthesized. Whereas with (CH3)3P = CH2 the transylidation reaction is very slow and simple addition with formation of sparingly soluble products prevails, the double ylide forms cyclic complexes quite readily. These ylide chelates were characterized by analytical and spectroscopic data. 
  Reference    Z. Naturforsch. 34b, 1218—1220 (1979); eingegangen am 18. Juni 1979 
  Published    1979 
  Keywords    Ylide Complexes, Phosphorus Ylides, Iridium Complexes, Organoiridium Compounds 
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 TEI-XML for    default:Reihe_B/34/ZNB-1979-34b-1218.pdf 
 Identifier    ZNB-1979-34b-1218 
 Volume    34 
3Author    H. Schmidbaur, A. MörtlRequires cookie*
 Title    Ein spiro-bicyclisehes Phosphor-ylid und sein korrespondierendes Phosphoniumkation A Spiro-bicyclic Phosphorus Yhde and its Corresponding Phosphonium Cation  
  Reference    Z. Naturforsch. 35b, 990—993 (1980); eingegangen am 19. Mai 1980 
  Published    1980 
  Keywords    Ylides, Phosphorus Ylides, Phosphonium Salts, Spiro-bicyclic Compounds 
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 TEI-XML for    default:Reihe_B/35/ZNB-1980-35b-0990.pdf 
 Identifier    ZNB-1980-35b-0990 
 Volume    35 
4Author    Annette Schier, Hubert SchmidbaurRequires cookie*
 Title    Derivate und Koordinationsverbindungen des Triphenylphosphoniumcyclopropylids (C6H5 )3P =C(CH2 )2  
 Abstract    Triphenylphosphonium cyclopropylide is converted into the corresponding 1-H-or 1 -D-cyclopropylphosphonium bromide in the reaction with HBr or DBr, respectively. With methyl iodide, the 1-methyl-cyclopropylphosphonium iodide is generated. Addition of BH3 (as THF -BH3) yields trihydrido-(l-triplienylphosphoniocyclopropyl)borate -(CH3)3A1 and (C2Hs)3Ga also give 1:1 adducts, the metal center being attached again to C-l of the cyclopropyl ring. -Complexes of AuCl, however, are easily transformed into ionic ] : 2 complexes, irrespective of the ratio of the reactants employed. Au(I) is two-coordinate in those complexes with two intact cyclopropylides as the sole ligands. -NMR data of all the new materials are presented. Einführung 
  Reference    Z. Naturforsch. 37b, 1518—1523 (1982); eingegangen am 9. August 1982 
  Published    1982 
  Keywords    Ylide Complexes, Triphenylphosphonium Cyclopropylide, Phosphorus Ylides, Gold Complex 
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 TEI-XML for    default:Reihe_B/37/ZNB-1982-37b-1518.pdf 
 Identifier    ZNB-1982-37b-1518 
 Volume    37 
5Author    Hansjörg GrützmRequires cookie*
 Title    Spaltung der Ylid-Bindung in Phosphor-Yliden: Photolyse von thiophosphoranylsubstituierten (Triphenylphosphoranyliden)methanen Cleavage of Ylidic Bonds in Phosphorus Ylides: Photolysis of Thiophosphoranyl-Substituted (Triphenylphosphoranylidene)methanes  
 Abstract    The thiophosphoranyl-substituted (triphenylphosphoranylidene)methanes 1, 6 a, b are cleaved photolytically (/ > 300 nm, 3 d, 0 °C) to yield triphenylphosphane and the thio-aza-phosphetanes 3 and 8 a, b, b', respectively. The formation of these heterocycles is explained in­ voking insertion o f the carbenes 2 and 7 a, b into the methine CH bond of one of the isopropyl groups. If 6a is irradiated for 16 h in the presence of the phosphanes P(NM e2)3, P(OMe)3 or P("Bu)3, the new ylides 9 a, b, c are obtained along with small quantities of 8 a. These results indicate a cleavage of the ylidic bond in 1 and 6a, b. The failure of attempted cyclopropana-tion reactions of olefins as well as the absence of the expected product o f a 1,2-H shift, 10, in the case of the photolysis of 6b leave doubts as to the occurrence of free carbenes. 
  Reference    Z. Naturforsch. 45b, 170—174 (1990); eingegangen am 26. Mai/23. August 1989 
  Published    1990 
  Keywords    Phosphorus Ylides, Photolysis, N M R Spectra, MS Spectra 
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 TEI-XML for    default:Reihe_B/45/ZNB-1990-45b-0170.pdf 
 Identifier    ZNB-1990-45b-0170 
 Volume    45 
6Author    HansH. Karsch, R. Oland Richter, A.Nnette SchierRequires cookie*
 Title    Tetra-heteroelementsubstituierte Methane und isomere Phosphorylide: C-versus P-Nucleophilie ambidenter Phosphinomethanide Tetra-H eteroelem ent Substituted M ethanes and Isomeric Phosphorus Ylides: C-versus P-Nucleophilicity of Am bidentate Phosphinomethanides  
 Abstract    Fully heteroelement substituted carbanions, i.e. phosphinomethanides of the type [(Me2P)C(X)(Y)]~ (X, Y = PMe2, SiMe3) react with organoelement chlorides (X -Cl, Y -C l) to give tetra-heteroelement substituted methanes and/or isomeric phosphorus ylides with an element-phosphorus bond. The latter in some cases are rigid, in others fluctional and in cer­ tain cases may rearrange to the isomeric methane derivatives. The results are explained by the involvement of pentacoordinated silicon derivatives, which only occur as transient spe­ cies, however. A compound with pentacoordinated silicon in the ground state is obtained from Li[(Me2P)2C(SiMe3)] and RSiCl3 (R = Ph), but it slowly rearranges to the isomeric methane derivate (Me2P)2(Me3Si)(Cl2PhSi)C within four weeks at + 20 °C. Within six weeks, further rearrangement occurs to give the ylide Me2P-PM e2=C(SiMe3)(SiPhCl2). For R = 'Bu, only the analogous rearranged ylide is found. Its molecular structure was confirmed by an X-ray structure determination. 
  Reference    Z. Naturforsch. 48b, 1533—1543 (1993); eingegangen am 9. Juli 1993 
  Published    1993 
  Keywords    Phosphinomethanes, Phosphinomethanides, Phosphorus Ylides, Skeleton Rearrangement 
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 TEI-XML for    default:Reihe_B/48/ZNB-1993-48b-1533.pdf 
 Identifier    ZNB-1993-48b-1533 
 Volume    48