- Room-temperature reduction of sulfur hexafluoride with metal phosphides
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Upon treatment with sulfur hexafluoride, alkali metal diphenyl or dicyclohexyl phosphides are oxidized within seconds to tetraphenyl or tetracyclohexyl diphosphines. When bulky di-tert-butylphosphide is employed, fluorophosphine intermediates are detected. This is the first reported reaction of sulfur hexafluoride with metal phosphides, and a rare example of reactivity of sulfur hexafluoride at ambient temperature. This journal is
- Huchenski, Blake S. N.,Speed, Alexander W. H.
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supporting information
p. 7128 - 7131
(2021/07/28)
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- Group 14 metal terminal phosphides: Correlating structure with |J MP|
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A series of heavier group 14 element, terminal phosphide complexes, M(BDI)(PR2) (M = Ge, Sn, Pb; BDI = CH{(CH3)CN-2,6-iPr 2C6H3}2; R = Ph, Cy, SiMe 3) have been synthesized. Two
- Tam, Eric C. Y.,Maynard, Nicola A.,Apperley, David C.,Smith, J. David,Coles, Martyn P.,Fulton, J. Robin
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p. 9403 - 9415
(2012/11/07)
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- 'Click' Dendritic phosphines: Design, synthesis, application in Suzuki coupling, and recycling by nanofiltration
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A new synthetic route towards stable molecular-weight enlarged monodentate phosphine ligands via 'click' chemistry was developed. These ligands were applied in the Pd-catalyzed Suzuki-Miyaura coupling of aryl halides and phenyl boronic acid. The supported systems show very similar activities compared to the unsupported analogues. Moreover, recycling experiments by means of nanofiltration using ceramic nanofiltration membranes demonstrate that these systems can be recovered and reused efficiently.
- Janssen, Michele,Mueller, Christian,Vogt, Dieter
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supporting information; experimental part
p. 313 - 318
(2009/10/20)
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- Highly efficient synthesis of (Phosphinodihydrooxazole)- (1,5-cyclooctadiene) Iridium complexes
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A highly efficient one-pot procedure for the synthesis of complexes of the type [Ir(COD)(Phox)]X, where Phox is a (chiral) phosphinooxazoline ligand, X = PF6 or B[(3,5-(CF3)2C6H 3)]4 (BARF), is developed. Former reported syntheses demanded the isolation of pure ligands by column chromatography, but the ligands tend to adsorb irreversibly on silica. Moreover, the chromatography has to be performed with careful exclusion of air. The present method avoids this difficulties. The yields of the syntheses are comparable with those starting from the pure ligands. The method is also suitable for the preparation of complexes of the type [Rh(COD)(Phox)]BARF and [Rh(Phox)2]BARF.
- Semeniuchenko, Volodymyr,Khilya, Volodymyr,Groth, Ulrich
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experimental part
p. 1147 - 1158
(2010/03/02)
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- Palladium catalysed alkyne hydrogenation and oligomerisation: A parahydrogen based NMR investigation
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The role phosphine ligands play in the palladium(ii)-bis-phosphine-hydride cation catalysed hydrogenation of diphenylacetylene is explored through a PHIP (parahydrogen induced polarization) NMR study. The precursors Pd(LL′)(OTf)2 (1a-e) [LL′ = dcpe (PCy2CH 2CH2PCy2), dppe, dppm, dppp, cppe (PCy 2CH2CH2PPh2)] are used. Alkyl palladium intermediates of the type [Pd(LL′)(CHPhCH2Ph)](OTf) (2 and 3) are detected and demonstrated to play an active role in hydrogenation catalysis. Magnetization transfer experiments reveal chemical exchange from the α-H of the alkyl ligand of 2a (LL′ = dcpe) and linkage isomer 2e′ (LL′ = cppe) into trans-stilbene on the NMR timescale. Activation parameters (ΔH≠ and ΔS≠) for this transformation have been determined. These experiments, coupled with GC/MS data, indicate that the catalytic activity is greater in methanol, where it follows the order: dcpe > cppe > dppp > dppe > dppm, than in CD 2Cl2. All five of the phosphine systems described are less active than those based on bcope [where bcope is (C8H 14)PCH2-CH2P(C8H14)] and tbucope [where tbucope is (C8H 14)PC6H4CH2P(tBu) 2]. cis, cis-1,2,3,4-Tetraphenyl-buta-1,3-diene is detected as a minor reaction product with Pd(LL′)(PhCH-CHPh-CPh=CHPh)+ (4) also being shown to play a role in the alkyne dimerisation step.
- Lopez-Serrano, Joaquin,Duckett, Simon B.,Dunne, John P.,Godard, Cyril,Whitwood, Adrian C.
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supporting information; body text
p. 4270 - 4281
(2009/02/03)
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- Sterically hindered iminophosphorane complexes of vanadium, iron, cobalt and nickel: a synthetic, structural and catalytic study
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Bis(aryliminophosphoranyl)alkanes L1 = (CH2)n(R12P=NR2)2 (n = 1 or 2, R1 = Ph or Me, R2 = Ph, C6H2Me3-2,4,6 or C6H3Pri2-2,6) reacted with cobalt and nickel dihalides to give chelate complex
- Al-Benna, Sarah,Sarsfield, Mark J.,Thornton-Pett, Mark,Ormsby, Daniel L.,Maddox, Peter J.,Bres, Philippe,Bochmann, Manfred
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p. 4247 - 4257
(2007/10/03)
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- Competing Radical, Carbanion, and Carbene Pathways in the Reactions of Hindered Primary Alkyl Halides with Lithium Dialkylamides
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A variety of methods were utilized to study the mechanism of reaction of 6-iodo-5,5-dimethyl-1-hexene and its bromo, chloro, and tosylate derivatives with LDA and several other lithium dialkylamides.In the reaction of 6-iodo-5,5-dimethyl-1-hexene with LDA in THF, radical, carbanion, and carbene pathways occured simultaneously.However, when the corresponding bromide was allowed to react with LDA, the radical pathway was minor and when the corresponding chloride or tosylate was allowed to react with LDA, no evidence for radical products was observed.This is the first time that competing radical, carbanion, and carbene pathways have been detected in the reaction of a primary alkyl halide with any nucleophile.
- Ashby, E. C.,Park, B.,Patil, G. S.,Gadru, K.,Gurumurthy, R.
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p. 424 - 437
(2007/10/02)
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- NOVEL ANIONIC CHALCOGENO LIGANDS. TELLUROPHOSPHINITES R2PTe- AND CHALCOGENOTELLUROPHOSPHINATES R2P(Ch)Te-
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Elemental tellurium reacts with diorganylphosphides R2P- to give tellurophosphinites R2PTe- and with chalcogenophosphinites R2PCh- to give chalcogenotellurophosphinates R2P(Ch)Te- R = C6H11, C6H5; Ch = O,S,Se,T
- Bildstein, Benno,Sladky, Fritz
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p. 341 - 347
(2007/10/02)
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- Preparation of optically active peralkyldiphosphines and their use, as the rhodium(I) complex, in the asymmetric catalytic hydrogenation of ketones
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Two types of the optically active peralkyldiphosphine, 2,3-O-isopropylidene-2,3-dihydroxy-1,4-bis(dialkylphosphino)butane (Rdiop 3) and N-(N'-substituted carbamoyl)-4-dicyclohexylphosphino-2-dicyclohexylphosphinomethylpyrrolidine (R-Cycapp 8), have been p
- Tani, Kazuhide,Suwa, Kenichi,Tanigawa, Eiji,Ise, Tomokazu,Yamagata, Tsuneaki,et al.
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p. 203 - 222
(2007/10/02)
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