Addition Compounds of Group V Pentahalides

Webster, Matthew P.

doi:10.1021/cr60239a004

Cited by 44 publications

(4 citation statements)

References 140 publications

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“…Webster 11 has reviewed the literature to 1965 on the addition compounds of group V pentahalides. That review covered both adduct and ionized species of phosphorus(V) pentahalides.…”

Section: Introductionmentioning

confidence: 99%

Neutral Six-Coordinate Phosphorus

1996

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“…Webster 11 has reviewed the literature to 1965 on the addition compounds of group V pentahalides. That review covered both adduct and ionized species of phosphorus(V) pentahalides.…”

Section: Introductionmentioning

confidence: 99%

Neutral Six-Coordinate Phosphorus

1996

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“…These data can be used to study the existence of a linear relation between ∆H • and ∆G • for the complexation of SbCl 5 . For example, PhCHO-SbCl 5 has a dipole moment of 8.65 D [37] while the dipoles of SbCl 5 and PhCHO are about 0 and 2.80 D, respectively. Only 84% of the variance of ∆H • is explained by ∆G • .…”

Section: The Donor Number Scale: Datamentioning

confidence: 99%

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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“…Es sind zahlreiche Addukte der Pniktidpentahalogenide beschrieben worden [2][3][4], mit einem Schwerpunkt bei den Antimon-Oxy-Addukten, wie z.B. (CH3)2SOSbCl5 [5,6] oder F2SOMF5, F2COMF5 (M = As, Sb) [7].…”

Section: Introductionunclassified

Methansulfinylchlorid-Lewissäure-Addukte CH₃S(Cl)OMF₅ (M = As, Sb) und Kristallstruktur von CH₃S(Cl)OSbCl₅ [1] / Methanesulfinylchloride Lewis Acid Adducts CH₃S(Cl)OMF₅ (M = As, Sb) and Crystal Structure of CH₃S(Cl)OSbCl₅ [1]

Minkwitz

Lohmann

Preut

1996

Zeitschrift Für Naturforschung B

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CH 3S(0)C1 reacts in HF as solvent with MF5 (M = As, Sb) to give products CH 3S(Cl)OMF5 (M = As, Sb). The new compounds are stable below 253 K and were charac terized by Raman and N M R spectroscopy.In addition, the crystal structure of C H 3S(Cl)OSbCl5 has been determinated. The complex crystallizes in the monoclinic space group P2x !n with a = 644. 3(5), b = 1905.9(14), c = 900.0(7) pm, ß = 99.27(6)° with four formula units per unit cell.Einleitung

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Addition Compounds of Group V Pentahalides

Cited by 44 publications

References 140 publications

Neutral Six-Coordinate Phosphorus

Neutral Six-Coordinate Phosphorus

The Donor Number or SbCl ₅ Affinity Scale

Methansulfinylchlorid-Lewissäure-Addukte CH₃S(Cl)OMF₅ (M = As, Sb) und Kristallstruktur von CH₃S(Cl)OSbCl₅ [1] / Methanesulfinylchloride Lewis Acid Adducts CH₃S(Cl)OMF₅ (M = As, Sb) and Crystal Structure of CH₃S(Cl)OSbCl₅ [1]

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Addition Compounds of Group V Pentahalides

Cited by 44 publications

References 140 publications

Neutral Six-Coordinate Phosphorus

Neutral Six-Coordinate Phosphorus

The Donor Number or SbCl 5 Affinity Scale

Methansulfinylchlorid-Lewissäure-Addukte CH3S(Cl)OMF5 (M = As, Sb) und Kristallstruktur von CH3S(Cl)OSbCl5 [1] / Methanesulfinylchloride Lewis Acid Adducts CH3S(Cl)OMF5 (M = As, Sb) and Crystal Structure of CH3S(Cl)OSbCl5 [1]

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The Donor Number or SbCl ₅ Affinity Scale

Methansulfinylchlorid-Lewissäure-Addukte CH₃S(Cl)OMF₅ (M = As, Sb) und Kristallstruktur von CH₃S(Cl)OSbCl₅ [1] / Methanesulfinylchloride Lewis Acid Adducts CH₃S(Cl)OMF₅ (M = As, Sb) and Crystal Structure of CH₃S(Cl)OSbCl₅ [1]