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'Phosphonium Salts' in keywords Facet   Publication Year 1982  [X]
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1Author    HansH. KarschRequires cookie*
 Title    Funktionelle Trimethylphosphanderivate, XVII [1]  
 Abstract    Methyl-bis(dimethylphosphinomethyl)phosphan, (Me2PCH2)2PMe Functional Derivatives of Trimethylphosphane, XVII [1] Methyl-bis(dimethylphosphinomethyl)phosphane, (Me2PCH2)2PMe (Me 2 PCH2)2PMe (3) is obtained from MePCl 2 (2a) or MeP(OPh) 2 (2b) and LiCH 2 PMe 2 (1). The oxides [Me 2 P(0)CH 2 ] 2 PMe (4) and [Me 2 P(0)CH 2 ] 2 P(0)Me (5), are formed on the reaction with air. Quaternisation with Mel gives the salts [(Me3PCH2)2PMe]l2 (6) and [(Me3PCH2)2PMe2]l3 (12). For comparison, also the isoelectronic (Me3SiCH2)2PMe (7), and (Me3SiCH2)2P 4 Bu (8), are synthesized and transformed to their methylphosphonium salts 10 and 11. WithCH 2 Br 2 , 3 forms the six-membered heterocycle [MeP(CH 2 PMe2)2CH 2 ]Br2 (13 a), which could not be isolated in a pure state, however. 3 may be metalated by LiBu: Li[Me2PCHP(Me)CH2PMe2] (15), is obtained, but a second metalation step could not be observed. The hydrolysis of 12 under unusual mild conditions (H2O or H2O/CH3OH) gives [Me2P(0)CH 2 PMe3]I (16), and [Me 4 P]I (17), as main products. Properties and NMR data of the new compounds are described. 
  Reference    Z. Naturforsch. 37b, 284—291 (1982); eingegangen am 12. Oktober 1981 
  Published    1982 
  Keywords    Triphosphane (PCPCP), Phosphonium Salts, Hydrolysis, NMR Spectra 
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 TEI-XML for    default:Reihe_B/37/ZNB-1982-37b-0284.pdf 
 Identifier    ZNB-1982-37b-0284 
 Volume    37 
2Author    Hubert Schmidbaur, Ulrich Deschler, Dietmar SeyferthRequires cookie*
 Title    Ylide Complexes of Alkali and Earth Alkaline Metals, VI [1] Neutral and Anionic Ferrocenylmethylides and Fluorenylides  
 Abstract    Coordination properties of phosphorus ylides towards electropositive metals are greatly improved in systems, where the carbanionic charge can be delocalized into the aromatic rings of substituents, as illustrated in the title compounds. The ferrocenyl-substituted ylide 2, synthesized from bis(diphenylphosphino)methane and (ferrocenyl)trimethyl-ammonium iodide via the phosphonium salt intermediate 1, is thus easily converted into the alkali complexes 3 a, b on treatment with NaNH2 or KH in tetrahydrofuran, respec-tively. The intensely coloured products are soluble in a number of organic solvents. NMR spectra of these solutions provide evidence for an interaction between alkali cations and the ferrocenyl rings. -From (C6H5)2CH2P(C6H5)2 and ferrocenylmethyl chloride a di-quaternary salt 4 is obtained, which yields a double-ylide mixture 5 a, b on treatment with base. Hydrolysis of tIiis product affords the ylidic phosphine oxide 6. -The reaction of the ylides 7 and 9 (described previously) with NaNHo, KH or barium metal (in liquid ammonia) leads to the (earth) alkali complexes 8a-c and 10a, b, respectively. With the exception of 8c, but similar to 3a, these materials contain tetrahydrofuran solvate molecules. The 23 Na NMR spectrum of 8a and the pronounced quadrupole broadening of the P(III) signals by the alkali cations in the 31 P NMR spectra of 8 a, b allow structural suggestions for the solution state as proposed in the formulae. Further treatment of 10b with KH yields a potassium complex 11, characterized, i.a.. via a corresponding diquaternary 
  Reference    Z. Naturforsch. 37b, 950—956 (1982); eingegangen am 2. März 1982 
  Published    1982 
  Keywords    Ylides, Alkali Complexes, Phosphonium Salts, Phosphonium Ferrocenylmethylides 
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 TEI-XML for    default:Reihe_B/37/ZNB-1982-37b-0950.pdf 
 Identifier    ZNB-1982-37b-0950 
 Volume    37