Reversing Lewis acidity from bismuth to antimony

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Abstract

Investigations on the boundaries between the neutral and cationic models of (Mesityl) ₂EX (E = Sb, Bi and X = Cl ⁻, OTf ⁻) have facilitated reversing the Lewis acidity from bismuth to antimony.

Abstract

Investigations on the boundaries between the neutral and cationic models of (Mesityl) ₂EX (E = Sb, Bi and X = Cl ⁻, OTf ⁻) have facilitated reversing the Lewis acidity from bismuth to antimony. We use this concept to demonstrate a higher efficiency of (Mesityl) ₂SbOTf over (Mesityl) ₂BiOTf in the catalytic reduction of phosphine oxides to phosphines. The experiments supported with computations described herein will find use in designing new Lewis acids relevant to catalysis.

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Covalent radii revisited.

Beatriz Cordero, Verónica Gómez, Ana E Platero-Prats … (2008)

A new set of covalent atomic radii has been deduced from crystallographic data for most of the elements with atomic numbers up to 96. The proposed radii show a well behaved periodic dependence that allows us to interpolate a few radii for elements for which structural data is lacking, notably the noble gases. The proposed set of radii therefore fills most of the gaps and solves some inconsistencies in currently used covalent radii. The transition metal and lanthanide contractions as well as the differences in covalent atomic radii between low spin and high spin configurations in transition metals are illustrated by the proposed radii set.

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Consistent van der Waals radii for the whole main group.

Manjeera Mantina, Adam C Chamberlin, Rosendo Valero … (2009)

Atomic radii are not precisely defined but are nevertheless widely used parameters in modeling and understanding molecular structure and interactions. The van der Waals radii determined by Bondi from molecular crystals and data for gases are the most widely used values, but Bondi recommended radius values for only 28 of the 44 main-group elements in the periodic table. In the present Article, we present atomic radii for the other 16; these new radii were determined in a way designed to be compatible with Bondi's scale. The method chosen is a set of two-parameter correlations of Bondi's radii with repulsive-wall distances calculated by relativistic coupled-cluster electronic structure calculations. The newly determined radii (in A) are Be, 1.53; B, 1.92; Al, 1.84; Ca, 2.31; Ge, 2.11; Rb, 3.03; Sr, 2.49; Sb, 2.06; Cs, 3.43; Ba, 2.68; Bi, 2.07; Po, 1.97; At, 2.02; Rn, 2.20; Fr, 3.48; and Ra, 2.83.