Tris(monochlorophenyl)- and Tris(dichlorophenyl)phosphines: Molecular Geometry, Anodic Behavior, and ESR Studies

Palau, Cecile; Berchadsky, Yves; Chalier, Florence; Finet, Jean‐Pierre; Gronchi, G.; Tordo, Paul

doi:10.1021/j100001a028

Cited by 38 publications

(21 citation statements)

References 3 publications

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“…The phosphane 5b could be integrated into the isosteric series of triarylphosphanes bearing one or no methyl substituent on the ortho-position of each phenyl ring, for which, in our previous studies,we had found a linear correlation between E p and the ∑σ + Hammett parameter. 1,2,26 However, 5a could not be integrated in this correlation and the ortho-hydroxymethyl substituent appeared to have a dramatic influence on its anodic potential value.…”

Section: Resultsmentioning

confidence: 95%

Synthesis, X-ray Geometry, and Anodic Behavior of Tris[2-(hydroxymethyl)phenyl]phosphane

et al. 1996

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Tris[(monohydroxymethyl)phenyl]phosphanes 5a and 5b were prepared, and the geometry of the ortho-isomer 5a was determined by X-ray diffraction. 5a was found to be propeller-like in shape, exhibiting a helical conformation with the three hydroxymethyl substituents standing on the same side as that with the phosphorus lone pair. Phosphanes 5a and 5b underwent electrochemical one-electron oxidation, giving rise to nonpersistent phosphoniumyl cation radicals 5a ‚+ and 5b ‚+ . The low value of the anodic peak potential of 5a was explained by the fast decay of 5a ‚+ , which was rapidly rearranged to a phosphoranyl radical through the formation of a strong P-O bond. The fast oxidation of this intermediate phosphoranyl radical followed by a second cyclization led to the 1-[2-(hydroxymethyl)phenyl]spirobi[1H,3H-2,1-benzoxaphosphole] 7a, which was isolated in significant yield.

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Section: Resultsmentioning

confidence: 95%

Synthesis, X-ray Geometry, and Anodic Behavior of Tris[2-(hydroxymethyl)phenyl]phosphane

et al. 1996

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“…Another approach for assessing the nucleophilicity of the phosphines is to compare their HOMO energy, which was also assessed by DFT. 36,37 The nucleophilicity should increase with increasing -donor ability of the phosphines or, in other words, with increasing s-character of the orbital containing the lone pair, which should also be the HOMO of the molecule. A higher s-character of the HOMO, going in hand with a higher energy level of the HOMO, is thus indicative for a higher nucleophilicity.…”

Section: Resultsmentioning

confidence: 99%

Electron Rich Triarylphosphines as Nucleophilic Catalysts for Oxa-Michael Reactions

Fischer¹,

Renner²,

Boese³

et al. 2021

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Herein, we study the activity of methoxysubstituted arylphosphines (4-methoxy-phenyl)diphenylphosphine (MMTPP) and tris(4-trimethoxyphenyl)phosphine (TMTPP) in catalyzing oxa-Michael additions in comparison to commonly used triphenylphosphine (TPP). Acrylonitrile, acryl amide and divinyl sulfone are used as Michael acceptors and propargyl alcohol, allyl alcohol, n-propanol and i-propanol are assessed as Michael donors. In many cases, catalyst loadings of only 1 mol% in respect to the Michael acceptor are sufficient to provide full conversion towards the Michael adduct in 24 h at room temperature. Generally, TMTPP is the most active catalyst in all cases. The experimental activity trend was rationalized by calculating the Michael acceptor affinities of all phosphine – Michael acceptor combinations. Besides this parameter, the acidity of the alcohol has a strong impact on the reaction speed. The oxidation stability of the phosphines was evaluated and electron richest TMTPP was found to be only slightly more sensitive to oxidation than TPP. Finally, the catalysts were employed in the oxa-Michael polymerization of 2-hydroxyethyl acrylate. With TMTPP polymers characterized by number average molar masses of about 1200 g/mol at room temperature are accessible. Polymerizations carried out at 80 °C resulted in macromolecules containing a considerable share of Rauhut-Currier type repeat units and consequently lower molar masses were obtained.

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“…Different methods have been reported to determine the electronic properties of phosphines. The σ-donor ability increases when the s-character of the lone pair of the phosphine decreases, which is associated with a higher energy level of the HOMO [ 47 , 48 ]. Thus, DFT studies have been performed in order to calculate the energy level of the HOMO of compound 1 and compare it with other triarylphosphines which were also calculated.…”

Section: Resultsmentioning

confidence: 99%

A SF5 Derivative of Triphenylphosphine as an Electron-Poor Ligand Precursor for Rh and Ir Complexes

et al. 2020

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The synthesis of the triarylphosphine, P(p-C6H4SF5)3 containing a SF5 group, has been achieved. The experimental and theoretical studies showed that P(p-C6H4SF5)3 is a weaker σ-donor when compared with other substituted triarylphosphines, which is consistent with the electron-withdrawing effect of the SF5 moiety. The studies also revealed a moderate air stability of the phosphine. The σ-donor capabilities of P(p-C6H4SF5)3 were estimated from the phosphorus-selenium coupling constant in SeP(p-C6H4SF5)3 and by DFT calculations. The behavior of P(p-C6H4SF5)3 as ligand has been investigated by the synthesis of the iridium and rhodium complexes [MCl(COD){P(p-C6H4SF5)3}], [MCl(CO)2{P(p-C6H4SF5)3}2] (M = Ir, Rh), or [Rh(µ-Cl)(COE){P(p-C6H4SF5)3}]2, and the molecular structures of [IrCl(COD){P(p-C6H4SF5)3}] and [Rh(µ-Cl)(COE){P(p-C6H4SF5)3}]2 were determined by single X-ray diffraction. The structures revealed a slightly larger cone angle for P(p-C6H4SF5)3 when compared to other para-substituted triarylphosphines.

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Tris(monochlorophenyl)- and Tris(dichlorophenyl)phosphines: Molecular Geometry, Anodic Behavior, and ESR Studies

Cited by 38 publications

References 3 publications

Synthesis, X-ray Geometry, and Anodic Behavior of Tris[2-(hydroxymethyl)phenyl]phosphane

Synthesis, X-ray Geometry, and Anodic Behavior of Tris[2-(hydroxymethyl)phenyl]phosphane

Electron Rich Triarylphosphines as Nucleophilic Catalysts for Oxa-Michael Reactions

A SF5 Derivative of Triphenylphosphine as an Electron-Poor Ligand Precursor for Rh and Ir Complexes

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