4451-96-1Relevant academic research and scientific papers
Rhodium (thiophosphinoyl)(trimethylsilyl)methanide and bis(thiophosphinoyl) methanide complexes: S～S vs. C～S coordination
Heuclin, Hadrien,Carenco, Sophie,Le Goff, Xavier-Frederic,Mezailles, Nicolas
experimental part, p. 1453 - 1461 (2012/06/05)
A comparative study of the coordination modes of a (thiophosphinoyl) (trimethylsilyl)methanide (1-·Li+) and bis(thiophosphinoyl)methanide (2-·Li+) ligand with RhI was carried out. Several complexes we
Palladium and platinum units grafted on the periphery of carbosilane dendrimers
Benito, Monica,Rossell, Oriol,Seco, Miquel,Muller, Guillermo,Ordinas, Juan I.,Font-Bardia, Merce,Solans, Xavier
, p. 2477 - 2487 (2007/10/03)
The reaction of a series of phosphanyl-terminated carbosilane dendrimers with palladium and platinum complexes was carried out. The new metallodendrimers containing PdCl(η3-2-MeC3H4) and PtCl2 or Pt(C≡CPh)2 as peripheral groups were characterized by 1H, 13C, 29Si, 31P, and 195Pt NMR spectroscopy, and, in some cases, by mass spectrometry. The PtCl2-containing species of the second-generation carbosilane dendrimer displays only one of the two possible stereoisomers. By comparison with the 31P NMR spectra of the model compounds cis-[PtCl2(PPh2CH2 SiMe3)2] (4) and cis-[PtCl2{Me2Si(CH2 PPh2)2}] (5), it was deduced that the PtCl2 units are bound on the surface of the dendrimer through two phosphorus atoms belonging to the same branch. The palladium dendrimers were tested as catalysts in the hydrovinylation of styrene, and their activity was compared with that of the model catalyst [PdCl(η3-2-MeC3H4) (PPh2CH2SiMe3)]. The crystal structures of 4, 5, and [Pt(C≡CPh)2{Me2Si(CH2 PPh2)2}] (6) were solved by X-ray diffraction analysis. Wiley-VCH Verlag GmbH, 69451 Weinheim, Germany, 2002.
Reactions of α-lithiated phosphimines with PhCN; the crystal structure of (tmen)>2 (tmen = Me2NCH2CH2NMe2)
Hitchcock, Peter B.,Lappert, Michael F.,Wang, Zhong-Xia
, p. 1953 - 1956 (2007/10/03)
Treatment of the α-lithiated phosphinimine Li with benzonitrile yielded (via a trimethylsilyl or hydrogen 1,3 C -> N shift) the trimethylsilyliminophosphoranylenamidolithium complex Li (R = Me, R' = SiMe3 1; R = Ph, R' = SiMe3 2; or R = Ph, R' = H 3).Complex 2 was transformed into the corresponding potassium complex 4 by an exchange reaction with KOBut.Crystallisation of 4 from hexane in the presence of Me2NCH2CH2NMe2 (tmen) gave the tmen adduct 5 and a trace of the partially hydrolysed product (tmen)>2 6, which was characterised by a single crystal X-ray diffraction study as a dinuclear complex with each of the two potassium atoms in a different co-ordination environment.Complex 1 or 2 was hydrolysed to form the neutral iminophosphoranylenamine N(SiMe3)C(Ph)C(H)P(R)2N(SiMe3)H 7 or 8, which also showed (1H NMR spectroscopy) the presence of hydrogen bonds.
The Reaction of Diphenyl(trimethylsilylmethyl)phosphine with Carbonyl Compounds in the Presence of Fluorides
Kawashima, Takayuki,Mitsuda, Noriaki,Inamoto, Naoki
, p. 708 - 710 (2007/10/02)
Diphenyl(trimethylsilylmethyl)phosphine (1) was allowed to react with benzophenone in the presence of CsF in N,N-dimethylformamide to give a mixture of methyldiphenylphosphine (2), (2,2-diphenyl-2-trimethylsiloxyethyl)diphenylphosphine (3) and (2-hydroxy-2,2-diphenylethyl)diphenylphosphine (4) in good yield.The use of about 10 molpercent of CsF gave 3 with fairly good selectivity.The reaction with benzaldehyde gave a similar result, but only protodesilylation occurred in the reaction with enolizable carbonyl compounds.
Ambivalent Reactions of Phosphanes Metallated in α-Position with n-Butyllithium
Appel, Rolf,Haubrich, Gerhard,Knoch, Falk
, p. 2063 - 2075 (2007/10/02)
The reaction of diphenyl(trimethylsilylmethyl)phosphane (1) with n-butyllithium yields the lithium methanide 2, which reacts with chlorotrimethylsilane to form diphenylphosphane (3).Repeated lithiation yields the ambivalent inte
Some phosphorus Derivatives
Eaborn, Colin,Retta, Negussie,Smith, J. David
, p. 905 - 910 (2007/10/02)
Treatment of Li with PPh2Cl gave the phosphine PPh2, which, in spite of the steric crowding caused by the silicon ligand, was readily converted into the phosphonium salts Ph2H>I and Ph2Me>I; the latter on heating gave the ylid MePh2PC(SiMe3)2.In methanol at room temperature the phosphine PPh2 readily loses one Me3Si group to give PPh2; the remaining Me3Si groups are lost successively, with decreasing ease, giving finally PPh2Me.These Si-C bond cleavages are catalysed by acid but inhibited by base, and it is suggested that the initial step is protonation of the phosphine.The quaternary salt Ph2Me>I successively loses its Me3Si groups very readily in methanol, ultimately to give I.
Phosphinoalkylsilanes: Synthesis and Spectroscopic Properties of Phosphino(sylil)methanes, 1-Phosphino-2-silylethanes, and 1-Phosphino-3-silylpropanes
Holmes-Smith, Rupert D.,Osei, Rexford D.,Stobart, Stephen R.
, p. 861 - 866 (2007/10/02)
Synthesis of thirty-three compounds Ph2P(CH2)nSiXYZ (n=1, 2, or 3) and Me2P(CH2)2SiXYZ in which X, Y, or Z=H, Me, Ph, or Cl has been accomplished by (a) reaction at -78 deg C in tetrahydrofuran between alkyl(chloro)silanes and Ph2PCH2Li*tmeda for n = !, o
