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Lewis acid softness

Nonaqueous Bases Nonaqueous Nucleophiles Organometallic Catalytic Reduction Acidic Reduction Basic or Neutral Reduction Hydride Reduction Lewis Acids Soft Acids Radical Addition Oxidizing Agents... [Pg.406]

I K . 2.1. Classification of sonic metals according to ionic potential and Lewis acid softness (tiansilion metals arc in oxidation stale 1 II). (Reprinted l>y permission of Oxford University Press, t m hi i (i. Sposito, lhc Chemistry of Soils, Oxford University Press, New York, 19X0.)... [Pg.41]

PG Single elec. Red. Hydride Rediiclions Acid and Lewis Acid Soft Acids Free Rad. Rxn Oxidants ... [Pg.999]

The equilibrium constant of this reaction has been measured for a variety of metal cations in aqueous solutions and is known to correlate positively with both ionic potential and Lewis acid softness. As the ionic potential increases, the intensity of the positive coulomb field of the cation increases and repulsion of a solvating water proton becomes more likely. As the Lewis acid softness increases, the covalency of the M—O bond in a solvation complex increases and electron density is withdrawn from the O—H bond, thereby promoting the loss of the proton. [Pg.71]

The Hard-Soft-Add-Base (HSAB) theory was developed by Pearson in 1963. According to this theory, Lewis acids and Lewis bases are divided into two groups on one hand hard acids and bases, which are usually small, weakly polarizable species with highly localised charges, and on the other hand soft acids and bases which are large, polarizable species with delocalised charges. A selection of Lewis acids, ordered according to their hardness in aqueous solution is presented in Table 1.3. [Pg.28]

Lewis acid and the ligand. By contrast, soft-soft interactions are mainly enthalpic in origin and are characterised by a negative change in entropy" ... [Pg.29]

The most effective Lewis-acid catalysts for the Diels-Alder reaction are hard cations. Not surprisingly, they coordinate to hard nuclei on the reacting system, typically oxygen atoms. Consequently, hard solvents are likely to affect these interactions significantly. Table 1.4 shows a selection of some solvents ranked according to their softness. Note that water is one of the hardest... [Pg.29]

Donor strengths, taken from ref. 207b, based upon the solvent effect on the symmetric stretching frequency of the soft Lewis acid HgBr2. Gutmann s donor number taken from ref 207b, based upon AHr for the process of coordination of an isolated solvent molecule to the moderately hard SbCL molecule in dichioroethane. ° Bulk donor number calculated as described in ref 209 from the solvent effect on the adsorption spectrum of VO(acac)2. Taken from ref 58, based on the NMR chemical shift of triethylphosphine oxide in the respective pure solvent. Taken from ref 61, based on the solvatochromic shift of a pyridinium-A-phenoxide betaine dye. [Pg.30]

Analogous to the classification of Lewis acids and bases in hard and soft species, Ahrland et al. have su ested a division of donors and acceptors into classes a and 6. See Ahrland, S. Chatt, J. Davies, N.R. Quart. Rev. 1958, 77, 265... [Pg.42]

The mineral talc is extremely soft (Mohs hardness = 1), has good sHp, a density of 2.7 to 2.8 g/cm, and a refractive index of 1.58. It is relatively inert and nonreactive with conventional acids and bases. It is soluble in hydroduoric acid. Although it has a pH in water of 9.0 to 9.5, talc has Lewis acid sites on its surface and at elevated temperatures is a mild catalyst for oxidation, depolymerization, and cross-linking of polymers. [Pg.301]

Unsaturated sugars are useful synthetic intermediates (11). The most commonly used are the so-called glycals (1,5- or 1,4-anhydroalditol-l-enes). In the presence of a Lewis-acid catalyst, 3,4,6-tri-0-acetyl-l,5-anhydro-2-deoxy-D-arabinohex-l-enitol [2873-29-2] commonly called D-glucal triacetate, adds nucleophiles in both kineticaHy controlled and thermodynamically controlled (soft bases predominately at C-3 and hard bases primarily at C-1) reactions (11,13). [Pg.482]

R. G. Pearson, J. Am. Chem. Soc. 85 3533 (1963) T. L. Ho, Hard and Soft Acids and Bases in Organic Chemistry, Academic Press, New York, 1977 W. B. Jensen, The Lewis Acid-Base Concept, Wiley-Interscience, New York, 1980, Chapter 8. [Pg.21]

The strength of the complexation is a function of both the donor atom and the metal ion. The solvent medium is also an important factor because solvent molecules that are potential electron donors can compete for the Lewis acid. Qualitative predictions about the strength of donor-acceptor complexation can be made on the basis of the hard-soft-acid-base concept (see Section 1.2.3). The better matched the donor and acceptor, the stronger is the complexation. Scheme 4.3 gives an ordering of hardness and softness for some neutral and ionic Lewis acids and bases. [Pg.234]

With soft Lewis acids, phenotellurazines 43 form molecular complexes in which the tellurium center serves as the ligating atom [82DOK(266)1164 85KGS757]. The 1 1 complexes 49 are formed with salts of Hg(II) and Ag(I). PdCb reacts with 43 to give 1 2 complexes 50. Whereas the Hg(II) and Pd(II) complexes are stable on exposure to air, the Ag(I) complexes rapidly decompose when isolated from their solutions. [Pg.20]

For the activation of a substrate such as 19a via coordination of the two carbonyl oxygen atoms to the metal, one should expect that a hard Lewis acid would be more suitable, since the carbonyl oxygens are hard Lewis bases. Nevertheless, Fu-rukawa et al. succeeded in applying the relative soft metal palladium as catalyst for the 1,3-dipolar cycloaddition reaction between 1 and 19a (Scheme 6.36) [79, 80]. They applied the dicationic Pd-BINAP 54 as the catalyst, and whereas this type of catalytic reactions is often carried out at rt or at 0°C, the reactions catalyzed by 54 required heating at 40 °C in order to proceed. In most cases mixtures of endo-21 and exo-21 were obtained, however, high enantioselectivity of up to 93% were obtained for reactions of some derivatives of 1. [Pg.237]

Continuum effects indicated by hard and soft acid-base (Lewis acids) and bases. C. K. Jorgensen, Top. Curr. Chem., 1975,56,1-66 (210). [Pg.60]

In recent studies, we found that primary and secondary amines, alone or somehow faster in the presence of the soft Lewis acid Ag+ (refs. 7-9) substitute the bromine in (S)-2-bromopropanamides, in an organic solvent, at room temperature, and yield N-alkyl-, and N,N -dialky 1-aminopropanamides, with inversion of configuration and high enantiomeric excess. Conversely, in the presence of silver oxide (Ag20), much faster reactions occur with retention of configuration, giving... [Pg.161]

Lewis Acids and Bases Hard and Soft Acids and Bases... [Pg.338]

Once acids and bases have been classified as hard or soft, a simple rule can be given hard acids prefer to bond to hard bases, and soft acids prefer to bond to soft bases (the HSAB principle)P The rule has nothing to do with acid or base strength but merely says that the product A—B will have extra stability if both A and B are hard or if both are soft. Another rule is that a soft Lewis acid and a soft Lewis base... [Pg.341]


See other pages where Lewis acid softness is mentioned: [Pg.72]    [Pg.72]    [Pg.130]    [Pg.131]    [Pg.131]    [Pg.132]    [Pg.146]    [Pg.72]    [Pg.72]    [Pg.130]    [Pg.131]    [Pg.131]    [Pg.132]    [Pg.146]    [Pg.719]    [Pg.9]    [Pg.164]    [Pg.165]    [Pg.169]    [Pg.380]    [Pg.21]    [Pg.236]    [Pg.8]    [Pg.2]    [Pg.11]    [Pg.152]    [Pg.246]    [Pg.502]    [Pg.50]    [Pg.110]    [Pg.98]   
See also in sourсe #XX -- [ Pg.71 , Pg.146 ]




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