- Photochemical reactions of triplet phenylphosphinidene with carbon monoxide and nitric oxide
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Here we report the photochemical reactions of triplet phenylphosphinidene with carbon monoxide and nitric oxide. The photolysis of phenylphosphirane in carbon monoxide-doped matrices enabled the first spectroscopic identification of phenylphosphaketene, t
- Mardyukov, Artur,Niedek, Dominik
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- A new stereoselective synthesis of phosphiranes
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The synthesis of phosphiranes from primary phosphines and diol ditosylates was found to be stereoselective, and chiral phosphiranes were prepared from optically pure diols. The four optical isomers of 1-mesityl-2,3-dimethylphosphirane, (2S,3S)-(+)-3, (2R,3R)-(-)-4, anti-cis-(meso)-5, and syn-cis-(meso)-6, were all synthesized from mesitylphosphine and the corresponding diol ditosylates. Compound 6 was unstable, but compounds 3, 4, and 5 were all isolated in pure form. Their structure assignments were based on the NMR coupling constants JP-H and JP-C. The phosphiranes were transformed into tungsten pentacarbonyl complexes. Tungsten tetracarbonyl-triphenylphosphine complexes (22, 23, 24) of compounds 3, 4, and 5 were synthesized in high yields by the reaction of the phosphiranes and W(CO)4(PPh3)(THF). The absolute stereochemistry of the phosphiranes 3, 4, and 5 was determined by X-ray crystal structure analysis of compounds 22, 23, and 24. Stereochemical effects on NMR coupling constants and mass spectra of the phosphiranes are discussed.
- Li, Xinhua,Robinson, Kerry D.,Gaspar, Peter P.
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- Preparation and Characterization of Parent Phenylphosphinidene and Its Oxidation to Phenyldioxophosphorane: The Elusive Phosphorus Analogue of Nitrobenzene
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Triplet phenylphosphinidene was prepared by light-induced elimination of ethylene from the corresponding phenylphosphirane and was characterized by IR and UV/vis spectroscopy together with matching of its spectral data with density functional theory computations. The photolysis of phenylphosphirane in 3P-O2 doped matrices enabled the spectroscopic identification of a hitherto unknown phenyldioxophosphorane, the long elusive phosphorus analogue of nitrobenzene.
- Mardyukov, Artur,Niedek, Dominik,Schreiner, Peter R.
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- Direct Syntheses of 1-Phenylphosphetane and 1-Phenylphosphirane. Crystal and Molecular Structures of Cyclotrimerisation Precursor Complexes and
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Dilithium phenylphosphide reacts with 1,3-dichloropropane or 1,2-dichloroethane to give 1-phenylphosphetane or 1-phenylphosphirane, respectively; the free phosphines have been used to prepare the cyclotrimerisation precursor complexes and formu
- Kang, Yew Beng,Pabel, Michael,Willis, Anthony C.,Wild, S. Bruce
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p. 475 - 476
(2007/10/02)
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- METALLA IV-b-PHOSPHOLANNES II-METALLA-2 (OXA-, THIA- ou AZA-)-3 PHOSPHOLANNES
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2-sila-, germa- or stanna- 3-(oxa-, thia- or aza-) phospholanes have been synthesized by reactions of dihalometalla-IV-b compounds with dilithiated β-phosphorus alcohols, thiols or amines HYCH2CH2P(H)Ph (Y=O, S, NMe).Germa- and stanna- heterocycles can also be obtained from germyl- or stannyldiamines and the same β-phosphorus alcohols, thiols or amines. 2-sila 3-(oxa- or thia-) phospholanes are of particular interest for their decomposition reaction leading to silanone or silathione and phosphirane.
- Andriamizaka, J. D.,Escudie, J.,Couret, C.,Satge, J.
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p. 279 - 286
(2007/10/02)
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