Enthalpies de complexation de quelques phosphoramides avec le chlorure d'antimoine(V). Influence de la structure sur le nombre donneur selon Gutmann

Bollinger, Jean‐Claude; Yvernault, Germaine; Yvernault, Théophile

doi:10.1016/0040-6031(83)80264-0

Cited by 12 publications

(9 citation statements)

References 25 publications

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“…Conductivity measurements show ions formation in the presence of acetonitrile,51 tertiary phosphines,52 acetic anhydride,53 and other donors.6' It is of particular interest to discuss the cases of triethylamine and HMPA of dubious DN values. Bollinger et al 44 found that triethylamine is rapidly quaternized by 1,2dichloroethane under the catalytic action of SbCl5 as suggested earlier by Taft et al;68 in similar concentrations (2.2 X 10~2 mol-L-1) 1,2-dichloroethane solutions of SbCl5 + Et3N and of (47) Gutmann, V.; Mairinger, F.; Winkler, H. Monatsh. Chem.…”

Section: Discussionmentioning

confidence: 65%

A Lewis basicity scale for nonprotogenic solvents: enthalpies of complex formation with boron trifluoride in dichloromethane

Maria¹,

Gal²

1985

J. Phys. Chem.

180

143

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Section: Discussionmentioning

confidence: 65%

A Lewis basicity scale for nonprotogenic solvents: enthalpies of complex formation with boron trifluoride in dichloromethane

Maria¹,

Gal²

1985

J. Phys. Chem.

180

143

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“…[27] The title of the Cataldo article draws a special attention on TEPA, owing to the biological effects and other applications of TEPA and its analogs, as mentioned above. The initially published DN value for TEPA of 383 kJ mol À 1 (DN = 91.5 kcal mol À 1 ) [25] is considerably higher than expected. A revised value of 209.2 kJ mol À 1 (50 kcal mol À 1 ) was proposed by Cataldo, on the basis of several corrections, in particular a hypothetical ring opening of aziridinyl groups during the calorimetric measurements.…”

Section: Introductionmentioning

confidence: 65%

“…In contrast, the calorimetric measurements with BF 3 are carried out by injection of the gas in an excess of base until saturation of the solution, equivalent to a titration, which allows the determination of the stoichiometry of the adduct . As another possible source of error on DN, it was also suggested that ionization of SbCl 5 in excess may occur in the presence of strong bases …”

Section: Resultsmentioning

confidence: 99%

“…papers and books, and also from other authors for the phosphoramides. [24,25,26] The DN values published by Gutmann and coll. were reported without explicit uncertainty and experimental conditions, which are usually difficult to trace.…”

Section: Experimental Secion Experimental Datamentioning

confidence: 99%

“…[b] From Ref. [25]; uncertainties estimated from published data. [c] Experimental À ΔH for reaction (2), but in DCM solution, Ref.…”

Section: )(Dcm) [D] G4mentioning

confidence: 99%

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On the Lewis Basicity of Phosphoramides: A Critical Examination of Their Donor Number through Comparison of Enthalpies of Adduct Formation with SbCl₅and BF₃

et al. 2019

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The Lewis basicity of a series of phosphoryl compounds was examined using DFT and ab initio methods, including solvation effects. The enthalpies of adduct formation with two archetypal Lewis acids, antimony pentachloride and boron trifluoride, used to define the donor number DN and the BF3 affinity (BF3A) respectively, were examined. The BF3 adducts allow the use of the high‐accuracy G4 approach, whereas for SbCl5 adducts, three different DFT formalisms, including empirical dispersion corrections, were used because the G4 formalism is not available for third‐row elements. For a comparison with experimental data, solvation effects were taken into account by using the polarizable continuum model. The experimental BF3 affinities were well reproduced by G4 calculations when including PCM solvation. Conversely, comparisons of our calculated values and experimental results reported in the literature show that SbCl5 enthalpies for phosphoramides are in error. In particular the DN for HMPA should be revised.

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The Donor Number or SbCl ₅ Affinity Scale

Laurence

Gal

2009

Lewis Basicity and Affinity Scales

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The first calorimetric measurements on the reaction of SbCl 5 with Lewis bases in solution seem to have been made in 1963 by Olofsson [1]. Later, this author published a series of papers between 1963 and 1973 on the enthalpy of complexation of SbCl 5 with numerous carbonyl bases [2][3][4][5][6][7][8][9][10][11], and also a few ethers [11,12], methanol [12], water [13] and nitrobenzene [11]. Gutmann extended this series to a host of different Lewis bases [14,15] and proposed, in 1966, the concept of donor number (DN) [16][17][18] to express quantitatively the Lewis basicity of solvents. Although the DN scale has been proposed and extensively used [19-21] as a solvent parameter, it relies on measurements made on dilute solutions of bases. It is, therefore, a solute scale and not a solvent scale of Lewis affinity. Structure of SbCl 5 ComplexesThe SbCl 5 molecule shows D 3h symmetry in its trigonal bipyramidal configuration. By complexation with one molecule of Lewis base, B, it distorts to an irregular octahedron as shown by the X-ray structures of the solid complexes listed in Table 2.1.The X-ray structure of a representative complex is shown in Figure 2.1. It can be seen that the Sb O bond of the HCONMe 2 -SbCl 5 complex [22] is much shorter (2.048Å) than the sum of the van der Waals radii (2.2 + 1.4 = 3.6Å) and slightly longer than the sum of the covalent radii (1.41 + 0.56 = 1.97Å) of the antimony and oxygen atoms. The Sb O vector points in the direction of a putative sp 2 lone pair of oxygen (SbOC = 124.5 • ). The preferred lone pair of oxygen is the less sterically hindered one, on the hydrogen side.Interestingly, SbCl 5 coordinates to the nitrogen and not to the sulfur atom of the polyfunctional bases S 2 N 2 (CSD reference code GIRXEK) and S 4 N 4 [23]. According to the HSAB rule that hard acids prefer hard bases, and since nitrogen bases are classified as hard or borderline whereas sulfur bases are soft, this site preference enables SbCl 5 to be Lewis Basicity and Affinity Scales: Data and Measurement

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Enthalpies de complexation de quelques phosphoramides avec le chlorure d'antimoine(V). Influence de la structure sur le nombre donneur selon Gutmann

Cited by 12 publications

References 25 publications

A Lewis basicity scale for nonprotogenic solvents: enthalpies of complex formation with boron trifluoride in dichloromethane

A Lewis basicity scale for nonprotogenic solvents: enthalpies of complex formation with boron trifluoride in dichloromethane

On the Lewis Basicity of Phosphoramides: A Critical Examination of Their Donor Number through Comparison of Enthalpies of Adduct Formation with SbCl₅and BF₃

The Donor Number or SbCl ₅ Affinity Scale

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Enthalpies de complexation de quelques phosphoramides avec le chlorure d'antimoine(V). Influence de la structure sur le nombre donneur selon Gutmann

Cited by 12 publications

References 25 publications

A Lewis basicity scale for nonprotogenic solvents: enthalpies of complex formation with boron trifluoride in dichloromethane

A Lewis basicity scale for nonprotogenic solvents: enthalpies of complex formation with boron trifluoride in dichloromethane

On the Lewis Basicity of Phosphoramides: A Critical Examination of Their Donor Number through Comparison of Enthalpies of Adduct Formation with SbCl5and BF3

The Donor Number or SbCl 5 Affinity Scale

Contact Info

Product

Resources

About

On the Lewis Basicity of Phosphoramides: A Critical Examination of Their Donor Number through Comparison of Enthalpies of Adduct Formation with SbCl₅and BF₃

The Donor Number or SbCl ₅ Affinity Scale