Lewis acid basic interactions

Molecular interactions can be classified into non-polar (np), polar (p), and a third kind of forces called associative forces, which include Lewis acid basic interactions like hydrogen bonding ah). 

Steric interactions between bulky substituents such as t-Bu, leading to larger C-E-C bond angles, obviously affect the Lewis basicity caused by the increased -character of the electron lone pair. However, the strength of the Lewis acid-base interaction within an adduct as expressed by its dissociation enthalpy does not necessarily reflect the Lewis acidity and basicity of the pure fragments, because steric (repulsive) interactions between the substituents bound to both central elements may play a contradictory role. In particular, adducts containing small group 13/15 elements are very sensitive to such interactions as was shown for amine-borane and -alane adducts... 

Owing to the strength of the B—F bond, die BF3 complexes are of widespread use as model compounds, for investigating Lewis acid-base interactions and the nature of the donor-acceptor bond. BF3 is frequently employed as a standard Lewis acid, for the quantitative characterization of the Lewis basicity of donor mojecules.62,63 The gas-phase equilibrium constants for some BF3 complexes are shown in Table 5. 

The hypothesized delocalization of lone pair electrons in the above silicon compounds is supported by the lowered basicity of the silyl compounds as compared to the corresponding carbon compounds. This reduced basicity is contrary to that expected on the basis of electronegativity effects operating through the a system since silicon is less electronegative than carbon. It is consistent with an internal Lewis acid-base interaction between the nitrogen and oxygen lone pairs and empty acceptor d orbitals on the silicon. Experimentally this reduced basicity is shown by the absence of disiioxane adducts with BF3 and BO ... 

Using contact angle (see Basic Protocol 4), the quantitative determination on the basis of the Lifshiz-van der Waals and electron donor-acceptor of Lewis acid-base interactions contributing to surface tension was extended to proteins (van Oss et ah, 1981). Despite its relative simplicity, the method has not gained popularity in the application to food proteins directly, probably because of the lack of similarity with proteins in solutions as this method uses a semi-dried form of proteins. However, investigation of the quality of packaging material, such as permeation and absorption, may... 

Ionic liquids can be compared to any other liquid in that the reactivity of a species will depend upon its relative activity in solution. To this end it is important to consider the relative Lewis and Bronsted acids that can interact with the solutes to affect their activity. It is also important to remember that ionic liquids with discrete anions have wider potential windows and what we therefore hope to achieve with them is more susceptible to the presence of reactive species. The influence of impurities on the electrochemical behavior of an ionic liquid will depend upon the relative Lewis acidity/basicity of the liquid and of the redox process in question. Eutectic-based ionic liquids behave very differently from ionic liquids with discrete... 

The electron-withdrawing ability of the fluorine atom can draw electron density from an adjacent nitrogen atom, making a distant nitrogen more basic. A second effect is the shortening of the P—Cl bond in a P(F)C1 vs. a PCI2 center (32). Thus, an incoming Lewis acid will interact with the phosphazene at a site that is distant from the P(F)C1 site. 

Because of the rather localized negative charge at the phenoHc oxygen atom , the standard dye (44) is capable of specific HBD/HBA and Lewis acid/base interactions. Therefore, in addition to the nonspecific dye/solvent interactions, the betaine dye (44) predominately measures the specific HBD and Lewis acidity of organic solvents. On the other hand, the positive charge of the pyridinium moiety of (44) is delocalized. Therefore, the solvent Lewis basicity will not be registered by the probe molecule (44). If this solvent property is relevant for the system under study, other empirical measures of Lewis basicity should be used cf. Section 7.7. 

We would like to note that a related Lewis acid/base interaction with hydrides may also suffice the piupose of the assessment of basicity. The thermodynamic analyses of the hydride adduct formation with protic substrate is usually accomplished by spectroscopic investigations of their equilibria of formation (eq 7). 

LNA, which is an acid, can adsorb on alumina via acid-base interaction or hydrogen bonding. The structural formula of LNA and those of other organic dispersants are given in Fig. 2. The interaction between the solvent and LNA cannot be responsible for the viscosity curves because the most basic solvent, tetrahydrofuran (THF) [11], would interact with LNA the most. The acid-base interaction is based on Drago s work on Lewis acid-base interaction energies [12]. Fowkes [2,13,14] expanded the concept to ceramic processing. The relative acidity and basicity of solvents used are listed in Table 1. The ceramic powders used are listed in Table 2. 

The Lewis acidity/basicity of copper and nickel and ttieir oxides indicate that nickel oxide is the stronger acid and that both oxides are more acidic than the native metals. This implies that the acidic oxides should be better able to interact with the basic groups in the polyetherimide stractuie such as imide nitrogens or carbonyl oxygens. The oxides of copper and nickel also differ in their chemical reactivity and environmental stability. For example, copper oxides... 

Concepts of acidity and basicity are, in practice, defined and evaluated by their utility. Since overly formd definitions can be restrictive the concepts of acidity evolve towaids more comprehensive definitions. For example the Lewis definition includes the Broensted definition simply regarding the proton as an electron acceptor. Because the interaction of Broensted acids and bases in solutions involves a common process, protic transfer, scales of acidity can be established, for example the Hammett [1] acidity function. For Lewis acid-base interaction there is no common process to provide a unique basis for comparisons of acid strength. Experimentally, the strength of a Lewis acid depends upon the particular Lewis base. The classification of acids and bases as hard or soft in the principle of hard and soft acids and bases (HSAB principle) clarifies the interactions of Lewis acids and bases [2a]. Strong interactions occur between hard acid and hard base, or between soft acid and soft base, hi the hard-hard interaction there is a considerable electrostatic contribution to bonding and in the soft-soft interaction there is a major covalent contribution to bonding. The use of density functional analysis has clarified the concepts of hardness and softness and an empirical ranking of Lewis acids, based on local hardness is, proposed [2c]. 

The strength of Lewis acid-base interactions cannot be expressed in terms similar to the acidity and basicity constants. K. and of the Bronsted-Lowry theory. Consequently an equilibrium constant resembling the protolytic constant of Bronsted acid-base couples, Eq. (1), cannot be specified. Because of the broad variety of Lewis acid-base interactions there would be as many acid strength scales as there are interacting bases. 

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