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2000 (1)
1995 (1)
1Author    Jan Schneider, Eckhard Popowski, Normen PeuleckeRequires cookie*
 Title    Reaktionen der Lithiumhydridosilylamide Me2(H)Si-N(Li)R (R = CMe3, SiMe3) mit Chlortrimethylstannan und Chlormethylsilanen M e^ SiC l« {n = 1 -3) Reactions of Lithium Hydridosilylamides Me2(H)Si-N(Li)R (R = CMe3, SiMe3) with Chlorotrimethylstannane and Chloromethylsilanes Me4_" SiCl, in = 1 -3)  
 Abstract    The under reflux conditions in /7-octane stable lithium hydridosilylamides Me2(H)Si-N(Li)R (1: R = CM e3, 2: SiMe3) were allowed to react with chlorotrimethylstannane and chlorom e­ thylsilanes Me4_"SiCl" (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(SnM e3)SiMe3 (5), [Me2Si-NSiM e3]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 (M e3Sn)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 cor­ responding cyclodisilazanes [Me2Si-NR]2 3, 4, N-silylation products Me2(H)Si-N(SiM e2Cl)R 7b, 8b, and Me2(H)Si-N(SiMe2H)R 7c, 8c, and the silanes Me2SiHCl and M e2SiH2 are formed, the cyclodisilazanes being the main products. 1 and M eSiCl3 produce 3, Me2(H)Si-N(R')CM e3 (7d: R' = SiMeCl2, 7e: R' = SiMeCIH, 7f: R' = SiM eH2) and MeSiH3. In comparison with the reaction of 1 with Me2SiCl2 the yield o f cyclodisilazane is smaller and that of N-silylated compounds is higher. The reaction behaviour of 1 towards M e2SiCl2 and M eSiCl3 in THF is comparable to that in n-hexane. No silanimine intermediates are observed in the reactions of 1 or 2 with the chloromethylsi­ lanes Me4_,7SiCl" (n = 1 -3) in the molar ratios 1:5 and 1:10. 
  Reference    Z. Naturforsch. 55b, 924—934 (2000); eingegangen am 25. Mai 2000 
  Published    2000 
  Keywords    Hydridosilylamides, Cyclodisilazanes, Hydrogen-Chlorine-Exchange 
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 TEI-XML for    default:Reihe_B/55/ZNB-2000-55b-0924.pdf 
 Identifier    ZNB-2000-55b-0924 
 Volume    55 
2Author    Wolfgang Pohl, Ingo-Peter Lorenz, Heinrich Nöth, Martin SchmidtRequires cookie*
 Title    Offene und geschlossene Triferriophosphonium-Salze und Triferriophosphane O pen and Closed Triferriophosphonium Salts and Triferriophosphines  
 Abstract    The reaction of P(SiM e3)3 with an excess of C pFe(CO)2X (X = Cl, Br) through the action o f water gives the triferriophosphonium salt [{CpFe(CO)2}3PH]2FeX4 together with ferrocene as by-product. The cation of the salt can be deprotonated by D B U to afford the unstable triferriophosphine {CpFe(CO)2}3P. Its subsequent realkylation with RX (R = Me, CH2Ph; X = I, Br) leads to alkyltriferriophosphonium salts [{CpFe(CO)2}3PR]X. Photolysis of [{CpFe(CO)2}3PH]2FeX 4 induces the elimination of one CO group, and the CO-bridged and partly closed complex [{//-CO(CpFeCO)2}{CpFe(CO)2}PH]2FeX 4 is formed, the cation of which can also be deprotonated to give the corresponding m onobridged phosphine (w-CO(CpFeCO)2}{CpFe(CO)2}P. Both PH-phosphonium salts undergo a hydrogen-chlorine exchange reaction to give the P -C l analogues [{CpFe(CO)2}3PCl]2FeX4 and [{//-CO (CpFeCO)2}{CpFe(CO)2}PCl]2FeX 4. The IR and NM R spectra of all species as well as the X-ray structure analyses of the open and closed P -H functional com plexes are reported and discussed. 
  Reference    Z. Naturforsch. 50b, 1485—1493 (1995); eingegangen am 30. März 1995 
  Published    1995 
  Keywords    Iron, Tristrimethylsilylphosphine, Hydrogen Chlorine Exchange, X-Ray, Decarbonylation 
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 TEI-XML for    default:Reihe_B/50/ZNB-1995-50b-1485.pdf 
 Identifier    ZNB-1995-50b-1485 
 Volume    50