Etude De l'ACTION Du Soufre Sur La Tris(tertiobutyl)phenylphosphine

Navech, Jacques; Revel, M.; Kraemer, Raymond

doi:10.1080/03086648408073132

Cited by 16 publications

(3 citation statements)

References 13 publications

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“…Phosphaalkene 2. Phosphaalkene 2 was synthesized according to the literature ,, starting from Mes*PH 2 and N , N -dimethylacetamide dimethyl acetal and was purified by silica gel chromatography . The 31 P NMR shows a resonance at δ = 94.3 ppm, closer to the values for “classical” phosphaalkenes, thus showing a decreased electron density at phosphorus compared with bis(amino) substituted 1 .…”

Section: Resultsmentioning

confidence: 99%

Phosphaalkenes with Inverse Electron Density: Electrochemistry, Electron Paramagnetic Resonance Spectra, and Density Functional Theory Calculations of Aminophosphaalkene Derivatives

et al. 2003

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Cyclic voltammetry of Mes*PdC(NMe 2 ) 2 (1) and Mes*PdC(CH 3 )NMe 2 (2) shows that, in solution in DME, these compounds are reversibly oxidized at 395 and 553 mV, respectively. Electrochemical oxidation or reaction of 1 (or 2) with [Cp 2 Fe]PF 6 leads to the formation of the corresponding radical cation, which was characterized by its electron paramagnetic resonance (EPR) spectra. Experimental 31 P and 13 C isotropic and anisotropic coupling constants agree with density functional theory (DFT) calculations showing that the unpaired electron is strongly localized on the phosphorus atom, in accord with the description Mes*P • -(C(NMe 2 ) 2 ) + . Electrochemical reduction of 1 is essentially irreversible and leads to a radical species largely delocalized on the C(NMe 2 ) 2 moiety; this neutral radical results from the protonation of the phosphorus atom and corresponds to Mes*(H)P-• C(NMe 2 ) 2 . No paramagnetic species is obtained by reduction of 2. The presence of the amino groups, responsible for the inverted electron distribution at the P-C double bond (P --C + ), confers on 1 and 2 redox properties that are in very sharp contrast with those observed for phosphaalkenes with a normal π electron distribution (P + -C -): no detection of the radical anion but easy formation of a rather persistent radical cation. For 1, this radical cation could even be isolated as a powder, 1 •+ PF 6 -. As shown by DFT calculations, this behavior is consistent with the decrease of the double bond character of the phosphoruscarbon bond caused by the presence of the amino groups.

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Section: Resultsmentioning

confidence: 99%

Phosphaalkenes with Inverse Electron Density: Electrochemistry, Electron Paramagnetic Resonance Spectra, and Density Functional Theory Calculations of Aminophosphaalkene Derivatives

et al. 2003

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“…4,5 Thus far, modification of PTA has focused on alkylation of the phosphorus 6 or nitrogen 7 or modification of the "lower rim" of the ligand, i.e., the triazacyclohexane ring. [8][9][10][11] Figure 1 depicts an arrangement of PTA derivatives that have appeared in the literature including a ring-expanded ligand, 8 PASO 2 , 9,10 DAPTA, 11 and a "ring-opened" PTA derivative (RO-PTA). 6 With the exception of the RO-PTA derivative, these PTA derivatives involve modification of the triazacyclohexane ring of PTA and are reasonably distant from phosphorus and therefore any coordinated metal center.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and Coordination Chemistry of a Novel Bidentate Phosphine: 6-(Diphenylphosphino)-1,3,5-triaza-7-phosphaadamantane (PTA-PPh₂)

et al. 2006

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The upper rim of 1,3,5-triaza-7-phosphaadamantane (PTA) has been modified for the first time. Lithiation of PTA, with n-butyllithium, resulted in deprotonation of an alpha-phosphorus methylene and the formation of 1,3,5-triaza-7-phosphaadamantane-6-yllithium (PTA-Li). The chiral chelating phosphine 6-(diphenylphosphino)-1,3,5-triaza-7-phosphaadamantane (PTA-PPh2) was synthesized, in racemic form, by the reaction of PTA-Li with ClPPh2. PTA-PPh2 has been fully characterized in solution by multinuclear NMR spectroscopy and mass spectrometry and in the solid state by X-ray crystallography. The 31P NMR spectrum contains a pair of doublets at -19.8 and -100.1 ppm (d, (2)J(PP) = 65 Hz). Unlike PTA, the new bidentate phosphine, PTA-PPh2, is insoluble in aqueous solutions. Two group 6 metal carbonyl complexes, [M(CO)4(PTA-PPh2)] (M = W and Mo), were synthesized by the addition of PTA-PPh2 to cis-[M(CO)4(pip)2] and characterized by NMR spectroscopy, IR spectroscopy, and X-ray crystallography. Also reported are the solid-state structures of cis-[W(CO)4PTA2], cis-[W(CO)4(PTA)(PPh3)], and [W(CO)4DPPM] (DPPM = diphenylphosphinomethane). PTA-PPh2 appears to be sterically similar to and slightly more electron-donating than DPPM.

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“…The possible existence of the monomeric form of LR 1 in solution led us to start investigating the potential of LR as a dienenophile for [2 ‫ם‬ 4] cycloaddition reactions (Scheme 1) [1,10]. It has been reported that the stable monomeric dithioxo(tri-tertbutylphenyl)phosphorane reacts with 2,3-dimethyl-1,3-butadiene in a [4 ‫ם‬ 2] cycloaddition process [11][12][13], and LR, as a dipolarophile, undergoes [2 ‫ם‬ 3] cycloaddition reactions with stable 1,3-dipolar compounds [10]. However, to our knowledge, there have been no attempts to utilize LR as a dienenophile or as an electrophile in syntheses of biologically active phosphorus heterocycles with P-S bond incorporation, and no report on biological activity of phosphorus-containing heterocycles obtained by employing Lawesson's reagent.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of biologically active phosphorus heterocycles via cyclization reactions of Lawesson's reagent

Ren-Xi

Chen

et al. 1999

Heteroatom Chem.

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Etude De l'ACTION Du Soufre Sur La Tris(tertiobutyl)phenylphosphine

Cited by 16 publications

References 13 publications

Phosphaalkenes with Inverse Electron Density: Electrochemistry, Electron Paramagnetic Resonance Spectra, and Density Functional Theory Calculations of Aminophosphaalkene Derivatives

Phosphaalkenes with Inverse Electron Density: Electrochemistry, Electron Paramagnetic Resonance Spectra, and Density Functional Theory Calculations of Aminophosphaalkene Derivatives

Synthesis and Coordination Chemistry of a Novel Bidentate Phosphine: 6-(Diphenylphosphino)-1,3,5-triaza-7-phosphaadamantane (PTA-PPh₂)

Synthesis of biologically active phosphorus heterocycles via cyclization reactions of Lawesson's reagent

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Etude De l'ACTION Du Soufre Sur La Tris(tertiobutyl)phenylphosphine

Cited by 16 publications

References 13 publications

Phosphaalkenes with Inverse Electron Density: Electrochemistry, Electron Paramagnetic Resonance Spectra, and Density Functional Theory Calculations of Aminophosphaalkene Derivatives

Phosphaalkenes with Inverse Electron Density: Electrochemistry, Electron Paramagnetic Resonance Spectra, and Density Functional Theory Calculations of Aminophosphaalkene Derivatives

Synthesis and Coordination Chemistry of a Novel Bidentate Phosphine: 6-(Diphenylphosphino)-1,3,5-triaza-7-phosphaadamantane (PTA-PPh2)

Synthesis of biologically active phosphorus heterocycles via cyclization reactions of Lawesson's reagent

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Synthesis and Coordination Chemistry of a Novel Bidentate Phosphine: 6-(Diphenylphosphino)-1,3,5-triaza-7-phosphaadamantane (PTA-PPh₂)